CN111537651A - Method for detecting heavy oil pollutants in aquatic products - Google Patents
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Abstract
The invention provides a method for detecting heavy oil pollutants in aquatic products, which comprises the following steps: (1) pretreating a sample; (2) ultrasonic extraction and concentration; (3) and (3) carrying out qualitative detection and analysis by using a gas chromatography-mass spectrometry method, wherein the aquatic products comprise fishes, mollusks, shrimps, crabs and shellfish. The method for detecting the heavy oil pollutants in the aquatic products, provided by the invention, has the following beneficial effects: (1) the method solves the problem that the detection method is blank after the frozen and stored aquatic products are suspected to be polluted due to the leakage of marine heavy oil in the ocean fishing and transporting process; (2) the sample pretreatment process is simple, and the solvent and time are saved; (3) the sample qualitative method is simple and rapid, can accurately identify whether the sample is polluted by the heavy oil, can help enterprises to quickly judge whether aquatic products are polluted by the heavy oil, and has good comprehensive benefits by adopting targeted measures.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a method for detecting pollutants in a water product polluted by marine heavy oil in an ocean transportation process.
Background
With the continuous improvement of living standard and the optimization of consumption structure, especially food structure in some countries and regions, the protein intake source of people has gradually shifted from traditional cereal food to meat food, and the demand of aquatic products as one of the foods capable of providing high quality protein has increased greatly in recent years. While the ocean fishing is vigorously developed in China, the import trade quantity of aquatic products is continuously increased, and the trade scale is continuously enlarged. Displaying according to the data of the customs administration website: the import quantity of marine products of water in China in 1-12 months in 2019 reaches 444 ten thousand tons, the same ratio is increased by 30.59%, the import amount reaches 158.37 hundred million dollars, and the same ratio is increased by 31.83%. From the import varieties, the imports of prawns, cod, lobsters, cephalopods, crabs, salmon and the like are mainly imported in China, and Russia, Peru, Vietnam, Indonesia and the United states are main sources of imported aquatic products in China.
Ships required for ocean fishing and transportation activities of aquatic products often use heavy oil as fuel oil. The heavy oil is the residual heavy oil after extracting gasoline and diesel oil from crude oil, and is prepared with normal pressure oil, vacuum residuum, cracked diesel oil, catalytic diesel oil, etc. as main material and features high molecular weight and high viscosity. The heavy oil has a specific gravity of generally 0.82 to 0.95 and a specific heat of about 10,000 to 11,000kcal/kg, and mainly contains hydrocarbons, and further contains a part (about 0.1 to 4%) of sulfur and a trace amount of inorganic compounds.
During the running process of an ocean fishing vessel or a transport vessel, hundreds of tons of heavy oil are often loaded in a cabin. If equipment is accidentally broken down, oil leakage is caused, and aquatic products (mainly fish products) transported in the cabin refrigeration storage are often polluted. The pollution is divided into a plurality of conditions, the first is that leaked heavy oil directly contacts the surface of aquatic products, the second is that volatilized odor components (mainly petroleum hydrocarbon compounds) pollute the aquatic products in a cold storage after the heavy oil is leaked, and the third is that heavy oil on clothes or carrying tools causes contact type pollution to the aquatic products when workers on a ship deal with oil leakage faults and carry goods.
In the prior art, aiming at the detection of pollutants in aquatic products, detection objects are often fish living in polluted water areas or pesticide components remained in artificially cultured fish. Because the detected pollutants are mostly distributed in biological tissues in the aquatic products due to the influence of the water area environment in which the aquatic products grow, and the detected pollutants change along with the pollution condition of the water area and the growth time change of the aquatic products. For example, patent application CN 108107119a "a method for detecting chloramphenicol residues in aquatic products" requires the following detection steps: crushing, extracting, purifying, detecting and the like, wherein an extraction solvent involved in the method is prepared by ethyl acetate, ammonia water and sodium chloride according to a certain proportion, the purification process is quite complex, and the method comprises the steps of passing through an HLB solid-phase extraction column, fixing the volume and the like; in patent application CN 102393435, namely a method for detecting the content of trace algae toxins in aquatic products, a mixed solution of n-butanol-methanol and water in a certain proportion is required for extracting a sample, the detected sample is required to be dry powder, and enrichment and purification of the sample are required to be an enrichment method such as a C18 solid phase extraction column, so that the operation steps are very complicated; in patent application CN 107102074A, GC-MS analysis method for quantitatively analyzing polycyclic aromatic hydrocarbons in aquatic products utilizes gel permeation chromatography to carry out degreasing, then utilizes an alumina-silica gel composite chromatographic purification column to effectively extract polycyclic aromatic hydrocarbons, and utilizes gas chromatography and mass spectrometry to carry out quantitative analysis. In addition, charcot training and the like have published a method for extracting petroleum hydrocarbon in marine shellfish bodies by an accelerated solvent extraction method (see marine environmental science, 2013 (2): 300-303), the method comprises the steps of sample preparation, sample extraction, treatment of an extracting solution, preparation of a calibration curve and the like, soft tissues of shellfish samples need to be placed in a high-speed homogenizer for stirring in the step of sample preparation, and the defects of long time consumption and complex operation process exist.
The technical scheme of the patent application listed above and the reports of related journal documents are all used for detecting toxic and harmful pollutants in the growth process of aquatic products such as living fishes, and the detection of pollutants caused by fuel oil leakage after the aquatic products are captured and frozen is not involved, and meanwhile, the complex sample pretreatment method is not suitable for detecting heavy oil pollutants in the transportation process after the aquatic products are captured and frozen. In recent years, reports on the measurement of heavy oil in aquatic animals are rarely seen in foreign literature, but most of the heavy oil in water neutralized sediments is measured by adopting a standard BS EN14039-2004, acetone/n-heptane (1: 1, V/V) and microwave extraction (150 ℃,15min) to extract a sample, concentrating an extracting solution by using a rotary evaporator, adding n-heptane to the concentrated solution to reach a constant volume of 10m L, and measuring the content of Total Petroleum Hydrocarbons (TPH) of petroleum hydrocarbons C10-C40 by using a gas chromatograph. The method is also not suitable for detecting the heavy oil pollutants in the transportation process of the aquatic products after being captured and frozen.
Therefore, a method for detecting heavy oil pollutants in aquatic products in a targeted, effective, simple and rapid manner is urgently needed to be established at the present stage.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a method for detecting heavy oil pollutants in aquatic products, which is used to solve the problem in the prior art that in the ocean fishing transportation process, the frozen and stored aquatic products are suspected to be polluted due to leakage of heavy oil for ships, and then a detection method is lacked.
In order to achieve the above and other related objects, the present invention provides a method for detecting heavy oil-type contaminants in aquatic products, comprising the steps of: (1) pretreating a sample; (2) ultrasonic extraction and concentration; (3) and (3) carrying out qualitative detection and analysis by using a gas chromatography-mass spectrometry method, wherein the aquatic products comprise fishes, mollusks, shrimps, crabs and shellfish.
Further, the step (1) is specifically operated as follows: placing an aquatic product sample to be tested under a room temperature condition for unfreezing; the step (2) is specifically operated as follows: placing the unfrozen aquatic product sample in a beaker, adding an extraction solvent to ensure that the extraction solvent is over the sample, performing ultrasonic extraction for 0.5-1h at room temperature, transferring the sample into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; the step (3) is specifically operated as follows: filtering the extraction concentrated solution obtained in the step (2) by a 0.22 mu m or 0.45 mu m microporous filter membrane, transferring the filtered extraction concentrated solution into a sample injection vial, and analyzing by a gas chromatography-mass spectrometry combined method according to certain instrument conditions to obtain a GC-MS (gas chromatography-mass spectrometry) spectrum of a sample; the marine heavy oil sample for transporting the aquatic product sample is used as a reference substance, sample injection analysis is carried out under the same gas chromatography-mass spectrometry instrument condition as that for detecting the aquatic product extract concentrated solution, a GC-MS spectrum obtained by the aquatic product sample is compared with a GC-MS spectrum of the marine heavy oil sample obtained under the same instrument condition, and when the GC-MS spectrum obtained by the aquatic product sample contains a plurality of or all of heavy oil characteristic peaks, the detection result of the sample is judged to be positive, otherwise, the detection result of the sample is negative.
Further, the step (1) is specifically operated as follows: placing an aquatic product sample to be tested under a room temperature condition for unfreezing; the step (2) is specifically operated as follows: placing the unfrozen aquatic product sample in a beaker, adding an extraction solvent to ensure that the extraction solvent is over the sample, performing ultrasonic extraction for 0.5-1h at room temperature, transferring the sample into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; the step (3) is specifically operated as follows: filtering the extraction concentrated solution obtained in the step (2) by a 0.22 mu m or 0.45 mu m microporous filter membrane, transferring the filtered extraction concentrated solution into a sample injection vial, and analyzing by a gas chromatography-mass spectrometry combined method according to certain instrument conditions to obtain a GC-MS (gas chromatography-mass spectrometry) spectrum of a sample; the marine heavy oil sample for transporting the aquatic product sample is used as a reference substance, sample injection analysis is carried out under the same gas chromatography-mass spectrometry instrument condition for detecting the aquatic product extract concentrated solution, a GC-MS spectrum obtained by the aquatic product sample is compared with a GC-MS spectrum of the marine heavy oil sample obtained under the same instrument condition, when the GC-MS spectrum obtained by the aquatic product sample contains all heavy oil characteristic peaks, the detection result of the sample is judged to be positive, and otherwise, the detection result is negative.
Further, the heavy oil characteristic peak of the GC-MS spectrum refers to a chromatographic peak determined by comparing the GC-MS spectrum of a heavy oil sample with the GC-MS spectrum of the water product extraction concentrated solution which is not polluted by heavy oil; the preparation method of the extraction concentrated solution of the water product which is not polluted by the heavy oil is the same as the preparation method of the concentrated solution of the sample of the water product to be detected.
Further, the extraction solvent in the step (2) is selected from one of n-hexane, tert-butyl methyl ether, ethyl acetate or acetone.
Further, the instrument conditions for the gas chromatography-mass spectrometry combined analysis in the step (3) are as follows: chromatographic column TG-5(30 m.times.0.25 mm. times.0.25 μm) or DB-5(30 m.times.0.25 mm. times.0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (the purity is more than or equal to 99.99 percent), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and a programmed temperature rise condition: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; with the Selective Ion Monitoring (SIM) mode, the qualitatively selected ions were 57, 71, 85.
Further, in the step (3), when the gas chromatography column selects TG-5(30m × 0.25mm × 0.25 μm), the retention time of the heavy oil characteristic peak of the GC-MS spectrum includes: 23.01 plus or minus 0.02min, 23.85 plus or minus 0.02min, 24.55 plus or minus 0.02min, 24.88 plus or minus 0.02min, 25.25 plus or minus 0.02min, 25.65 plus or minus 0.02min, 26.09 plus or minus 0.02min, 26.60 plus or minus 0.02min and 27.20 plus or minus 0.02 min.
Further, the aquatic product is selected from hairtail, squid, yellow croaker, cod, sardine, shark, whale, salmon, tuna, sea bass, pacific saury, raja, eel, spanish mackerel, and yellow croaker.
Further, the heavy oil-type contaminants are selected from distillate type bunker fuel oil and residual type bunker fuel oil.
Furthermore, the indexes of the marine fuel oil meet the national standard GB 17411-2015 and the subsequent revision thereof.
As mentioned above, the detection method of heavy oil pollutants in aquatic products provided by the invention has the following beneficial effects: (1) the method well solves the problem that the detection method is blank after the frozen and stored aquatic products are suspected to be polluted due to leakage of marine heavy oil in the ocean fishing and transporting process; (2) the sample pretreatment process is simple, and the solvent and time are saved; (3) the sample qualitative method is simple and rapid, can accurately identify whether the sample is polluted by the heavy oil, has strong practicability, can help enterprises to quickly judge whether aquatic products are polluted by the heavy oil, and has good comprehensive benefits by adopting targeted measures.
Drawings
FIG. 1 shows GC-MS (retention time between 20 and 28 min) of the detection of normal squid (negative sample) not contaminated by heavy oil when n-hexane is used as extraction solvent.
FIG. 2 shows a GC-MS diagram (retention time between 20 and 30 min) of the detection of a marine heavy oil sample with n-hexane as an extraction solvent.
FIG. 3 shows a GC-MS diagram of the detection of normal squid (negative sample) not contaminated by heavy oil when t-butyl methyl ether is used to extract the solvent.
FIG. 4 shows GC-MS (retention time between 20 and 30 min) of detection of normal squid (negative sample) not contaminated by heavy oil when extracting solvent with tert-butyl methyl ether.
FIG. 5 shows a GC-MS diagram of the detection of a marine heavy oil sample when tert-butyl methyl ether is used as a solvent.
FIG. 6 shows a GC-MS diagram of the detection of heavy oil samples for ships (retention time between 20-30 min) when tert-butyl methyl ether is used as a solvent.
FIG. 7 shows a GC-MS diagram of the detection of normal squid (positive sample) contaminated with heavy oil when t-butyl methyl ether is used to extract the solvent.
FIG. 8 shows GC-MS (retention time between 20 and 30 min) of the detection of normal squid (positive sample) contaminated with heavy oil when extracting solvent with tert-butyl methyl ether.
FIG. 9 shows a GC-MS (gas chromatography-Mass spectrometer) graph (retention time between 20 min and 30 min) of a normal ray hole sample without heavy oil pollution when a tert-butyl methyl ether extraction solvent is used, and a chromatographic peak comparison graph of a ray hole sample added with a marine heavy oil sample.
FIG. 10 is a GC-MS graph showing the detection of squid samples in the simulation experiment of the exposure of heavy oil environment at room temperature (20 ℃).
FIG. 11 shows GC-MS (retention time between 20 and 30 min) of the detection of squid samples in the simulation experiment of the exposure of heavy oil environment at room temperature (20 ℃).
FIG. 12 is a GC-MS graph showing the detection of squid samples in a simulation experiment under the condition of refrigeration in a refrigerator (4 ℃) and exposure to a heavy oil environment.
FIG. 13 shows GC-MS (retention time between 20 and 30 min) of squid sample detection in simulation experiments of environmental exposure of heavy oil under refrigerator refrigeration conditions (4 ℃).
FIG. 14 shows a GC-MS diagram of the detection of squid samples in the simulation experiment of the exposure of heavy oil environment under the condition of freezing in a refrigerator (-20 ℃).
FIG. 15 shows GC-MS (retention time between 20 and 30 min) of squid sample detection in the simulation experiment of heavy oil environment exposure under refrigerator freezing conditions (-20 ℃).
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Example 1
Placing the whole squid sample to be tested under the freezing condition at room temperature, and naturally thawing; placing the unfrozen aquatic product in a beaker, adding n-hexane as an extraction solvent to ensure that the extraction solvent just submerges a sample, performing ultrasonic extraction for 0.5h at room temperature, transferring the extract liquid into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column TG-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, injection port temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; using a Selective Ion Monitoring (SIM) mode, qualitatively selecting ions as 57, 71 and 85, obtaining a GC-MS diagram of a sample, wherein a typical chromatographic peak is shown in figure 1 of the attached drawings of the specification;
taking a marine heavy oil sample for transporting aquatic product samples as a reference substance, taking normal hexane as a solvent, dissolving, passing through a 0.45 mu m microporous filter membrane, and carrying out sample injection analysis under the same gas chromatography-mass spectrometry instrument conditions: chromatographic column TG-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, injection port temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; adopting a Selective Ion Monitoring (SIM) mode, qualitatively selecting ions as 57, 71 and 85, and obtaining a GC-MS spectrum of the heavy oil for the ship, referring to figure 2 of the attached drawings of the specification;
comparing the characteristic peaks of the heavy oil in the graph 1 and the graph 2, the retention time of the marine heavy oil sample is 23.01 +/-0.02 min, 23.85 +/-0.02 min, 24.55 +/-0.02 min, 24.88 +/-0.02 min, 25.25 +/-0.02 min, 25.65 +/-0.02 min, 26.09 +/-0.02 min, 26.60 +/-0.02 min and obvious chromatographic peaks around 27.20 +/-0.02 min, and the squid sample does not have the characteristic peak of the heavy oil, so the judgment result is negative, namely the sample to be detected is not polluted by the heavy oil.
Example 2
Placing the whole squid sample to be tested under the freezing condition at room temperature, and naturally thawing; placing the unfrozen aquatic product in a beaker, adding tert-butyl methyl ether as an extraction solvent to ensure that the extraction solvent just submerges a sample, performing ultrasonic extraction for 1h at room temperature, transferring an extract liquid into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; using a Selective Ion Monitoring (SIM) mode to qualitatively select ions as 57, 71 and 85 to obtain GC-MS diagrams of the sample, referring to the diagrams of the figures 3-4 of the specification;
taking a marine heavy oil sample for transporting a aquatic product sample as a reference substance, taking tert-butyl methyl ether as a solvent, dissolving, passing through a 0.45 mu m microporous filter membrane, and carrying out sample injection analysis under the same gas chromatography-mass spectrometry instrument conditions: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; adopting a Selective Ion Monitoring (SIM) mode, qualitatively selecting ions as 57, 71 and 85, obtaining GC-MS diagrams of the heavy oil for the ship, and referring to figures 5 to 6 of the attached figures of the specification;
comparing the heavy oil characteristic peaks of the attached figures 3-4 and the attached figures 5-6, the retention time of the heavy oil sample for the ship is as follows: 23.01 plus or minus 0.02min, 23.85 plus or minus 0.02min, 24.55 plus or minus 0.02min, 24.88 plus or minus 0.02min, 25.25 plus or minus 0.02min, 25.65 plus or minus 0.02min, 26.09 plus or minus 0.02min, 26.60 plus or minus 0.02min and obvious chromatographic peaks near 27.20 plus or minus 0.02min, but the squid sample does not have the characteristic peak of the heavy oil, so the judgment result is negative, namely the sample to be detected is not polluted by the heavy oil.
Example 3
Placing the whole squid sample to be tested under the freezing condition at room temperature, naturally thawing, longitudinally cutting along the belly of the squid towards the tail wing, grasping the head, tearing off viscera from fish meat, cutting off the viscera at the back of the fish head by using scissors, taking the rest parts except the viscera as the sample to be tested, placing the sample to be tested in a beaker, adding tert-butyl methyl ether as an extraction solvent to ensure that the extraction solvent just submerges the sample, performing ultrasonic extraction for 1h at room temperature, transferring the extract into a round-bottomed flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron Impact (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; using a Selective Ion Monitoring (SIM) mode to qualitatively select ions as 57, 71 and 85 to obtain a GC-MS diagram of a sample, which is shown in figure 7 of the attached drawings of the specification;
taking a marine heavy oil sample for transporting a aquatic product sample as a reference substance, taking tert-butyl methyl ether as a solvent, dissolving, passing through a 0.45 mu m microporous filter membrane, and carrying out sample injection analysis under the same gas chromatography-mass spectrometry instrument conditions: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron Impact (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; a GC-MS diagram of the heavy oil for the ship, which is shown in the attached figure 8 of the specification, and adopts a Selective Ion Monitoring (SIM) mode and qualitatively selects ions as 57, 71 and 85;
comparing the heavy oil characteristic peaks in the attached figures 7 and 8, the retention time of the heavy oil sample for the ship is as follows: 23.01 plus or minus 0.02min, 23.85 plus or minus 0.02min, 24.55 plus or minus 0.02min, 24.88 plus or minus 0.02min, 25.25 plus or minus 0.02min, 25.65 plus or minus 0.02min, 26.09 plus or minus 0.02min, 26.60 plus or minus 0.02min and obvious chromatographic peaks near 27.20 plus or minus 0.02min, and the squid sample also has the characteristic peak of the heavy oil, so that the judgment result is positive, namely the transportation of the inspected sample is polluted by the heavy oil.
Example 4
Addition recovery experiment:
placing the whole skate sample to be tested under the freezing condition at room temperature, and naturally thawing; cutting part of tissue on the surface of a sample, adding tert-butyl methyl ether as an extraction solvent to ensure that the extraction solvent just submerges the sample, performing ultrasonic extraction for 1h at room temperature, transferring an extraction liquid into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron Impact (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; using a Selected Ion Monitoring (SIM) mode to qualitatively select ions as 57, 71 and 85 to obtain a GC-MS diagram of the sample, referring to the diagram of figure 9 in the attached drawings of the specification;
placing the uncontaminated whole raja porosa sample to be tested under the freezing condition at room temperature, and naturally thawing; and cutting part of fish tissue on the surface of the sample. A marine heavy oil sample (0.6 mg) used for transporting Raja porosa was accurately weighed and added to 200g of the stolen fish meat tissue. Adding tert-butyl methyl ether as an extraction solvent to ensure that the extraction solvent just submerges a sample, performing ultrasonic extraction for 1h at room temperature, transferring an extract liquid into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column TG-5(30 m.times.0.25 mm. times.0.25 μm) or DB-5(30 m.times.0.25 mm. times.0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron Impact (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; the GC-MS diagrams of the samples of the heavy oil in the additive were obtained using a Selected Ion Monitoring (SIM) mode with qualitatively selected ions of 57, 71, 85, see FIG. 9 of the drawings in the specification.
And (3) overlapping and comparing the heavy oil characteristic peaks of the two samples, wherein the retention time of the heavy oil characteristic peaks of the Raja porosa added with the marine heavy oil sample is 23.01 +/-0.02 min, 23.85 +/-0.02 min, 24.55 +/-0.02 min, 24.88 +/-0.02 min, 25.25 +/-0.02 min, 25.65 +/-0.02 min, 26.09 +/-0.02 min, 26.60 +/-0.02 min and 27.20 +/-0.02 min, and the obvious chromatographic peaks are existed near the blank Raja porosa sample without the heavy oil characteristic peaks.
Example 5
Heavy oil environment exposure simulation experiment:
200g of each of 3 parts of squid samples to be tested which are not polluted under the freezing condition, 2g of heavy oil samples are taken, three parts of squid samples and three parts of heavy oil samples are respectively and jointly placed in a closed container, and the three parts of squid samples and the three parts of heavy oil samples are placed under the room temperature condition (20 ℃), the refrigerator refrigeration condition (4 ℃) and the refrigerator freezing condition (-20 ℃) for standing.
After 24 hours, taking out a squid sample at room temperature (20 ℃), placing the squid sample in a beaker, adding tert-butyl methyl ether as an extraction solvent to ensure that the extraction solvent just submerges the sample, performing ultrasonic extraction at room temperature for 1 hour, transferring the extract into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; obtaining GC-MS spectra of the aquatic product by using a Selected Ion Monitoring (SIM) mode and qualitatively selecting ions as 57, 71 and 85, referring to figures 10-11 of the attached drawings of the specification;
after 72 hours, taking out the squid sample placed under the refrigeration condition (4 ℃) and the freezing condition (-20 ℃) of the refrigerator, and naturally unfreezing the squid sample at room temperature; putting the aquatic product into a beaker, adding tert-butyl methyl ether as an extraction solvent to ensure that the extraction solvent just submerges a sample, performing ultrasonic extraction for 1h at room temperature, transferring an extract liquid into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; filtering the obtained extraction concentrated solution by a 0.45 mu m microporous filter membrane, transferring the extraction concentrated solution into a sample injection vial, and carrying out gas chromatography-mass spectrometry analysis according to certain instrument conditions, wherein the instrument conditions of the gas chromatography-mass spectrometry are as follows: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; obtaining GC-MS spectra of the aquatic product by using a Selected Ion Monitoring (SIM) mode and qualitatively selecting ions of 57, 71 and 85, referring to figures 12-13 of the attached drawings of the specification;
taking a marine heavy oil sample for transporting the batch of aquatic product samples as a reference substance, taking tert-butyl methyl ether as a solvent, dissolving, passing through a 0.45 mu m microporous filter membrane, and carrying out sample injection analysis under the same gas chromatography-mass spectrometry instrument conditions: chromatographic column DB-5(30m × 0.25mm × 0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (purity is more than or equal to 99.99%), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and programmed temperature rise conditions: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; adopting a Selective Ion Monitoring (SIM) mode, qualitatively selecting ions as 57, 71 and 85, obtaining GC-MS diagrams of the heavy oil for the ship, and referring to figures 14-15 of the attached figures of the specification;
the detection result shows that the retention time of the characteristic peak of the heavy oil of the sample under the condition of room temperature (20 ℃) is 23.01 +/-0.02 min, 23.85 +/-0.02 min, 24.55 +/-0.02 min, 24.88 +/-0.02 min, 25.25 +/-0.02 min, 25.65 +/-0.02 min, 26.09 +/-0.02 min, 26.60 +/-0.02 min and obvious chromatographic peaks nearby 27.20 +/-0.02 min; however, the heavy oil characteristic peak of the heavy oil component is not detected in the samples under the refrigerator refrigeration condition (4 ℃) and the refrigerator freezing condition (-20 ℃), which indicates that the experimental method can detect the heavy oil odor component adsorbed by the squid.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for detecting heavy oil pollutants in aquatic products is characterized by comprising the following steps: (1) pretreating a sample; (2) ultrasonic extraction and concentration; (3) and (3) carrying out qualitative detection and analysis by using a gas chromatography-mass spectrometry method, wherein the aquatic products comprise fishes, mollusks, shrimps, crabs and shellfish.
2. The method for detecting heavy oil pollutants in aquatic products according to claim 1, wherein the step (1) specifically comprises the following operations: placing an aquatic product sample to be tested under a room temperature condition for unfreezing; the step (2) is specifically operated as follows: placing the unfrozen aquatic product sample in a beaker, adding an extraction solvent to ensure that the extraction solvent is over the sample, performing ultrasonic extraction for 0.5-1h at room temperature, transferring the sample into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; the step (3) is specifically operated as follows: filtering the extraction concentrated solution obtained in the step (2) by a 0.22 mu m or 0.45 mu m microporous filter membrane, transferring the filtered extraction concentrated solution into a sample injection vial, and analyzing by a gas chromatography-mass spectrometry combined method according to certain instrument conditions to obtain a GC-MS (gas chromatography-mass spectrometry) spectrum of a sample; the marine heavy oil sample for transporting the aquatic product sample is used as a reference substance, sample injection analysis is carried out under the same gas chromatography-mass spectrometry instrument condition as that for detecting the aquatic product extract concentrated solution, a GC-MS spectrum obtained by the aquatic product sample is compared with a GC-MS spectrum of the marine heavy oil sample obtained under the same instrument condition, and when the GC-MS spectrum obtained by the aquatic product sample contains a plurality of or all of heavy oil characteristic peaks, the detection result of the sample is judged to be positive, otherwise, the detection result of the sample is negative.
3. The method for detecting heavy oil pollutants in aquatic products according to claim 1, wherein the step (1) specifically comprises the following operations: placing an aquatic product sample to be tested under a room temperature condition for unfreezing; the step (2) is specifically operated as follows: placing the unfrozen aquatic product sample in a beaker, adding an extraction solvent to ensure that the extraction solvent is over the sample, performing ultrasonic extraction for 0.5-1h at room temperature, transferring the sample into a round-bottom flask, and performing rotary evaporation and concentration to 1-2mL to obtain an extraction concentrated solution; the step (3) is specifically operated as follows: filtering the extraction concentrated solution obtained in the step (2) by a 0.22 mu m or 0.45 mu m microporous filter membrane, transferring the filtered extraction concentrated solution into a sample injection vial, and analyzing by a gas chromatography-mass spectrometry combined method according to certain instrument conditions to obtain a GC-MS (gas chromatography-mass spectrometry) spectrum of a sample; the marine heavy oil sample for transporting the aquatic product sample is used as a reference substance, sample injection analysis is carried out under the same gas chromatography-mass spectrometry instrument condition for detecting the aquatic product extract concentrated solution, a GC-MS spectrum obtained by the aquatic product sample is compared with a GC-MS spectrum of the marine heavy oil sample obtained under the same instrument condition, when the GC-MS spectrum obtained by the aquatic product sample contains all heavy oil characteristic peaks, the detection result of the sample is judged to be positive, and otherwise, the detection result is negative.
4. The method for detecting heavy oil pollutants in an aquatic product according to claim 2 or claim 3, wherein the heavy oil characteristic peak of the GC-MS spectrum is a chromatographic peak determined by comparing the GC-MS spectrum of a heavy oil sample with the GC-MS spectrum of an aqueous product extraction concentrate which is not polluted by heavy oil; the preparation method of the extraction concentrated solution of the water product which is not polluted by the heavy oil is the same as the preparation method of the concentrated solution of the sample of the water product to be detected.
5. The method for detecting heavy oil pollutants in aquatic product according to claim 2 or claim 3, wherein the extraction solvent in the step (2) is selected from one of n-hexane, t-butyl methyl ether, ethyl acetate or acetone.
6. The method according to claim 2 or claim 3, wherein the conditions of the apparatus for gas chromatography-mass spectrometry combined analysis in step (3) are as follows: chromatographic column TG-5(30 m.times.0.25 mm. times.0.25 μm) or DB-5(30 m.times.0.25 mm. times.0.25 μm), no-split sample injection mode, sample inlet temperature 300 ℃, carrier gas: high-purity helium (the purity is more than or equal to 99.99 percent), a constant-current mode, a carrier gas flow rate of 1-2mL/min, and a programmed temperature rise condition: initial column temperature 50 ℃, maintain for 1min, then rise to 150 ℃ at 8 ℃/min, maintain for 5min, then rise to 300 ℃ at 3 ℃/min, maintain for 30min, sample size 1 μ L, ion source: electron impact ionization (EI); ion source temperature: 250 ℃; the temperature of the transmission line is 300 ℃; electron energy: 70 eV; solvent retardation: 17 min; with the Selective Ion Monitoring (SIM) mode, the qualitatively selected ions were 57, 71, 85.
7. The method for detecting heavy oil pollutants in aquatic products according to claim 6, wherein in the step (3), when TG-5(30m x 0.25mm x 0.25 μm) is selected as the gas chromatographic column, the retention time of the heavy oil characteristic peak of the GC-MS spectrum comprises: 23.01 plus or minus 0.02min, 23.85 plus or minus 0.02min, 24.55 plus or minus 0.02min, 24.88 plus or minus 0.02min, 25.25 plus or minus 0.02min, 25.65 plus or minus 0.02min, 26.09 plus or minus 0.02min, 26.60 plus or minus 0.02min and 27.20 plus or minus 0.02 min.
8. The method according to any one of claims 1 to 7, wherein the aquatic product is selected from hairtail, squid, yellow croaker, cod, sardine, shark, whale, salmon, tuna, sea bass, pacific saury, porker, eel, ray, and yellow croaker.
9. The method of any one of claims 1 to 8, wherein the heavy oil-type contaminants are selected from distillate bunker fuel oil and residual bunker fuel oil.
10. The method as claimed in any one of claims 1 to 9, wherein the indexes of the bunker fuel oil meet the national standards GB 17411-2015 and its subsequent revisions.
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