CN111034900A - Reduction method of prometryn in marine bivalve shellfish - Google Patents
Reduction method of prometryn in marine bivalve shellfish Download PDFInfo
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- CN111034900A CN111034900A CN201911389559.7A CN201911389559A CN111034900A CN 111034900 A CN111034900 A CN 111034900A CN 201911389559 A CN201911389559 A CN 201911389559A CN 111034900 A CN111034900 A CN 111034900A
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- marine bivalve
- bivalve shellfish
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- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 27
- 235000015170 shellfish Nutrition 0.000 title claims abstract description 17
- 230000009467 reduction Effects 0.000 title description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 230000015556 catabolic process Effects 0.000 claims abstract description 43
- 238000006731 degradation reaction Methods 0.000 claims abstract description 43
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002829 reductive effect Effects 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000012154 double-distilled water Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000000447 pesticide residue Substances 0.000 abstract description 6
- 235000013305 food Nutrition 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 235000016709 nutrition Nutrition 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241001441955 Argopecten irradians Species 0.000 description 6
- -1 hydroxyl radicals Chemical class 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- 238000002144 chemical decomposition reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000005949 ozonolysis reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000273 veterinary drug Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical group [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- ZCUQOPGIJRGJDA-UHFFFAOYSA-N 1-naphthalen-1-ylethane-1,2-diamine Chemical compound C1=CC=C2C(C(N)CN)=CC=CC2=C1 ZCUQOPGIJRGJDA-UHFFFAOYSA-N 0.000 description 1
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000237519 Bivalvia Species 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 235000020639 clam Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019784 crude fat Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/276—Treatment with inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for reducing prometryn in marine bivalve shellfish, belonging to the technical field of reducing food pesticide residues. The invention utilizes the combined action of direct oxidation of ozone molecules and indirect oxidation of active free radicals in ozone water to degrade. The final concentration of the ozone is controlled to be 4.0-4.2mg/L, and Na is adopted2CO3Or adjusting the pH value of the solution to 6-7 by citric acid, treating the solution system at 23-27 ℃ in a constant-temperature water bath environment for 20-40 minutes, and cleaning to obtain the marine bivalve shell product with greatly reduced prometryn residue. The method can safely and efficiently degrade prometryn residues in the marine bivalve shellfish, the degradation rate can reach more than 85 percent to the maximum extent, the structure of the product is kept from being damaged, the processing cost of the product is reduced, the added value of the product is improved, and in addition, the nutritional ingredients of the marine bivalve shellfish are kept to the maximum extent.
Description
Technical Field
The invention relates to the technical field of aquatic product pesticide residue reduction, and in particular relates to a method for reducing prometryn in marine bivalve shellfish.
Background
At present, methods for reducing aquatic product pesticide and veterinary drug residues mainly comprise an adsorption method and a degradation method. The adsorption method can be used for removing pesticide and veterinary drug, such as the entrainment method is mainly used for reducing the pesticide residue in agricultural products by adsorbing some substances with adsorbability, such as activated carbon, quartz sand, resin and the like. Degradation methods are divided into biodegradation, chemical degradation and physical degradation. The biodegradation comprises two modes of microbial conversion and enzyme engineering degradation; the physical degradation mainly comprises ultrasonic treatment, irradiation treatment and the like; the chemical degradation mainly comprises hydrolysis, oxidative decomposition, photochemical degradation and the like.
The main disadvantages of these commonly used pesticide residue reduction techniques are:
(1) there are some safety problems, e.g.60Co-gamma irradiation has potential safety hazard of isotope radiation, has higher requirement on an operation place and has influence on the health of operators;
(2) chemical degradation usually causes secondary pollution, thereby greatly limiting the wide application of chemical methods in degrading pesticide residues.
(3) Most degradation methods usually have a significant effect on the degradation of fluid substances and a large reduction in the effect of solid substances due to the difficulty of acting on the inside.
In view of the problem of secondary pollution caused by chemical degradation, people in the industry have been trying to find a substance and a method thereof that will not cause secondary pollution. However, after the ozone reacts with the pesticide, redundant ozone is decomposed into oxygen, and generated compounds are all water-soluble and can be removed by water cleaning, so that a good direction is provided for chemical degradation of pesticide residues.
With the use of a large amount of herbicide, aquatic products are threatened by the herbicide, and how to safely and efficiently eliminate the prometryn contained in marine bivalves, including bay scallops, clams, oysters and the like, is still a problem to be overcome.
Disclosure of Invention
The invention aims to provide a safe and efficient method for reducing prometryn residues in marine bivalve shellfish, which can not only not destroy the original product structure of the marine bivalve shellfish, but also reserve the nutrient components of the original product to the maximum extent.
In order to achieve the purpose, the following technical scheme is adopted:
a method for reducing prometryn in marine bivalve shellfish utilizes the combined action of direct oxidation of ozone molecules in ozone water and indirect oxidation of active free radicals to degrade.
A method for reducing prometryn in marine bivalve shells comprises the following steps:
1) opening an ozone generator, introducing ozone into the test container at a theoretical yield of 3g/h, receiving ozone by double distilled water, collecting ozone water after 5min of balance, measuring the concentration of ozone in water, and controlling the final concentration of ozone to be 4.0-4.2 mg/L;
2) adding fresh marine bivalve shellfish to be treated;
3) by using Na2CO3Or adjusting the pH value of the solution to 6-7 by citric acid;
4) the temperature of the solution system is 23-27 ℃ in a constant-temperature water bath environment;
5) and cleaning after 20-40 minutes of treatment to obtain the marine bivalve product with greatly reduced prometryn residue.
Preferably, the final concentration of ozone in the step 1) is 4.2 mg/L.
Preferably, the temperature in step 4) is 25 ℃.
Preferably, the time for the treatment in the step 5) is 30 minutes.
Compared with the prior art, the invention has the following beneficial effects:
1. can well degrade prometryn residue in the marine bivalve shellfish, and the maximum degradation rate can reach more than 85 percent.
2. The integral treatment of the marine bivalve shell keeps the structure of the product from being damaged, reduces the processing cost of the product and improves the added value of the product;
3. the nutrient components of the marine bivalve are maintained to the maximum, and compared before and after the marine bivalve sample is treated by ozone, the water content, ash content, crude fat content, crude protein content, total sugar content, fatty acid, mineral elements and vitamin content of the marine bivalve sample have no significant difference (p is more than 0.05).
Drawings
FIG. 1 is a graph showing the change in the hydroxyl radical content in water at different feed times.
FIG. 2 is a graph showing the change in the content of hydroxyl radicals in water when ozone is applied for 60 min.
FIG. 3 is a graph showing the comparison of the turbidity of ozonated water with ozone introduced for various periods of time after terephthalic acid addition.
FIG. 4 is a graph comparing the superoxide radical absorbance of ozone water at different ozone introduction times.
FIG. 5 is a graph showing comparison of colors of ozone water for different ozone supply times.
FIG. 6 is a standard graph of superoxide radicals.
FIG. 7 is a graph showing the effect of ozone water on prometryn degradation after TBA is added.
FIG. 8 is a graph of the effect of different treatment times on degradation rate.
FIG. 9 is a graph showing the effect of ozone concentration on prometryn degradation rate.
FIG. 10 is a graph showing the effect of different temperatures on prometryn degradation efficiency.
FIG. 11 is a graph showing the effect of pH on prometryn degradation efficiency.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the practice of the invention is not limited thereto.
EXAMPLE 1 ozone Water preparation and degradation of ozone molecules and active substances
1. Determination of ozone concentration
An ozone generator (Qingdao Xinmei purification equipment Co., Ltd.) was started, ozone was introduced into the test vessel at a theoretical yield of 3g/h, and the volume of double distilled water receiving ozone was 1L. And (5) after balancing for 5min, beginning to collect ozone water, and measuring the ozone concentration in the water. The method for measuring the ozone concentration comprises the following steps: adding 20mL of 20% potassium iodide solution into a 250mL iodine measuring flask, adding 100mL of ozone generated by an ozone generator, uniformly mixing, adding 5mL of 3mol/L sulfuric acid solution, adding 1mL of 0.5% starch solution when titrating to be nearly colorless by using 0.005mol/L sodium thiosulfate standard solution, continuously titrating to be colorless, and calculating the content of ozone.
The relationship between the ozone supply time and the concentration of ozone water is shown in Table 1.
TABLE 1
As is apparent from Table 1, the concentration of dissolved ozone in the aqueous solution was continuously increased as the time for which ozone was introduced into the water was prolonged, and the ozone concentration reached 4.2mg/L when the introduction time was 30 min.
2. Determination of hydroxyl radical
The hydroxyl radical reacts with terephthalic acid to generate fluorescent substance dihydroxy terephthalic acid, and a strong fluorescence peak is generated at the excitation wavelength of 313nm and the emission wavelength of 420 nm. The stronger the fluorescence intensity, the more OH radicals are generated in the system.
Preparing 3, 5, 10, 20, 30 and 60min, 6 ozone water with different gradient concentrations, taking terephthalic acid with the concentration of 3.0mmol/L as a probe molecule, and enabling the pH value of the solution to be 11. V, ozone water: v probe molecular solution 3:1, 4mL quartz fluorescence cuvette, assay.
The hydroxyl radical is detected by using an F-320 fluorescence spectrophotometer, the result is shown in figure 1, the fluorescence intensity is continuously enhanced along with the increase of the ozone introducing time, and the OH radical generated in the system is continuously increased, so that the highest peak is reached under the wavelength of 420 nm. And (3) detecting the sample with the ozone for 60min, wherein the fluorescence intensity is changed after the ozone is introduced for 60min and is obviously enhanced compared with the fluorescence intensity when the ozone is introduced for 3-30 min. Further, the comparison and observation of the ozone water with different ozone introduction time is carried out, when the same amount of terephthalic acid is added, the turbidity of the terephthalic acid can be obviously different by naked eyes, as shown in figure 3, after 3-30min of ozone introduction, the terephthalic acid is added, and the ozone water is kept in a transparent and clear state. And adding terephthalic acid after 60min of ozone introduction, wherein the ozone water is milk white solution with suspended substances.
3. Determination of superoxide anion
Reaction of superoxide anion with hydroxylamine hydrochloride to produce NO2-，NO2-Under the action of sulfanilamide and naphthyl ethylenediamine hydrochloride, red azo compound is generated, which has a characteristic absorption peak at 530nm according to A530The value can be calculated as O in the sample2-And (4) content.
The determination method comprises the following steps: (1) extraction of superoxide anion: preparing 3, 5, 10, 20, 30 and 60min ozone water with 6 different gradient concentrations for determination. (2) Measurement operation table: a. preheating the spectrophotometer for more than 30min, adjusting the wavelength to 530nm, and adjusting the distilled water to zero. b. Preparing standard solution, namely taking a proper amount of sodium nitrite standard solution, firstly diluting the sodium nitrite standard solution to 625nmol/mL by 16 times, then diluting the sodium nitrite standard solution to 312.5, 156.25, 78, 39, 19.5, 9.765 and 4.9nmol/mL by times, and drawing a standard curve by using 156.25, 78, 39, 19.5, 9.765 and 4.9nmol/mL standard tubes. The procedure for the sodium nitrite standard curve preparation is shown in table 2.
TABLE 2
Mixing, and water bathing at 37 deg.C for 20min
Mixing, centrifuging at 25 deg.C and 8000rpm for 5min, carefully sucking upper water phase 1mL, adjusting to zero with distilled water, measuring A in 4mL glass cuvette530. Only one tube is needed for each test blank tube. The results of the spectrophotometric measurements are shown in FIG. 4, where the peak height of the characteristic absorption peak at 530nm increases continuously as the ozone introduction time increases from 3min to 60min, indicating that O is generated in the system2-The number of free radicals is increasing. As shown in FIG. 5, the color of the ozone water with different ozone supply times is more intense and the red color of the ozone water is also increased as the ozone treatment time is increasedAssists and proves O generated in the system2-The fact that the amount of free radicals increases.
A proper amount of sodium nitrite standard solution is diluted to be 0.0049, 0.009765, 0.0195, 0.039, 0.078 and 0.15625 mu mol/mL gradient diluted standard solution in a multiple ratio, and then the light absorption value of each concentration is measured. The mass concentration (x) of the sodium nitrite standard sample is used as an abscissa, and the corresponding absorbance (y) at the early 530nm wavelength is used as an ordinate to draw a standard curve as shown in fig. 6, and the standard curve is used as a basis to detect the concentration of superoxide radicals in the ozone water at different introduction times, and the result is shown in table 3.
TABLE 3
It can be concluded from table 3 that the superoxide radical content in the ozone water is increasing with increasing time of superoxide introduction. When the ozone treatment time is 60min, the content of the superoxide radical in the ozone water reaches 0.0286 mu mol/mL.
4. Effect of active substances in ozone water on degrading prometryn
In order to reveal whether the ozone water has selective direct oxidation of ozone molecules or non-selective free radicals generated by ozonolysis on prometryn, an ion scavenger Tertiary Butyl Alcohol (TBA) is added into the reaction solution to scavenge the free radicals generated by ozonolysis, thereby inhibiting the oxidation of the free radicals on prometryn. TBA with different concentrations is added into an ozone water system, and the degradation effect of various components on prometryn is analyzed by taking ozone water without TBA as a contrast, and the result is shown in figure 7, wherein as the addition amount of TBA is increased, the degradation rate of prometryn in different treatment times is reduced. The active free radicals in the ozone water are removed along with the addition of the TBA, only ozone molecules are used as active components, and the efficiency of degrading prometryn is greatly reduced. In contrast, the control group without TBA had ozone molecules, hydroxyl radicals, superoxide radicals and other active ingredients, and the degradation efficiency was greatly improved. It can be concluded that the ozone molecules and the radicals together play an oxidizing role in the whole oxidation system.
Further analysis of the proportional relationship of the components in the ozonated water in the degradation of prometryn is shown in table 4, and the data in table 4 show that: when 1000mg/L of TBA is added into the ozone water, most of active free radicals in the ozone water are basically eliminated, and compared with a control without the TBA, the degradation efficiency of the ozone molecule alone on prometryn is between 43.40% and 52.11%, and the degradation efficiency of the free radicals on prometryn is between 47.89% and 56.60%. It was shown that the ozone molecules and the active radicals each exert about 50% of the degradation effect in the degradation of prometryn. Meanwhile, table 4 also shows that as the treatment time of the ozone water increases, the ratio of the ozone molecules to act gradually increases, and the effect of the radicals gradually decreases.
The above data indicate that the major active species in the ozone water is O3、·OH、O2-In the process of degrading prometryn by ozone water, direct ozone oxidation and indirect free radical oxidation exist simultaneously to play a role together.
Example 2 Effect of degradation time on prometryn degradation Rate
The test method comprises the following steps: fresh Argopecten irradians → soaking in clear water for 72h → soaking in standard prometryn water solution with different concentrations at 0 deg.C for 72h → placing in ozone water under different experimental conditions → removing shell, pulping → extracting, purifying, concentrating → passing through membrane → detecting by gas chromatography.
The initial mass concentration of prometryn standard is selected as follows: 0.01, 0.05, 0.10, 0.20 and 0.30mg/kg, and the results of 3, 5, 10, 15, 20, 30 and 60min of degradation are shown in FIG. 8, the degradation rate reaches the maximum when the degradation is carried out for 30min, and the degradation efficiency of prometryn is not obviously increased when the sampling treatment time is increased from 30min to 60min, particularly at low concentration. Therefore, in consideration of efficiency and cost, the treatment time of 30min is ideal in practical production.
Example 3 Effect of ozone concentration on prometryn degradation Rate
The test method comprises the following steps: fresh Argopecten irradians → soaking in clear water for 72h → soaking in standard prometryn water solution with different concentrations at 0 deg.C for 72h → placing in ozone water under different experimental conditions → removing shell, pulping → extracting, purifying, concentrating → passing through membrane → detecting by gas chromatography.
The ozone concentration is selected as follows: 0.6, 1.2, 1.8, 3.0 and 4.2mg/L as the test concentrations, the results are shown in FIG. 9, the degradation efficiency of prometryn is enhanced by the extension of the ozone water treatment time with the increase of the ozone water concentration, and the degradation efficiency of prometryn in bay scallops by the ozone water can reach 84.97% when the ozone concentration is 4.2mg/L and the treatment time is 30 min.
Example 4 Effect of temperature on the degradation Rate of prometryn
The test method comprises the following steps: fresh Argopecten irradians → soaking in clear water for 72h → soaking in standard prometryn water solution with different concentrations at 0 deg.C for 72h → placing in ozone water under different experimental conditions → removing shell, pulping → extracting, purifying, concentrating → passing through membrane → detecting by gas chromatography.
The test results are shown in fig. 10 when 5 ℃, 15 ℃, 25 ℃ and 35 ℃ are selected, and it can be seen from fig. 10 that the degradation of prometryn by ozone is affected by the temperature, and the degradation rate of prometryn is always improved when the temperature is increased from 5 ℃ to 25 ℃ in the low temperature range. This is because an increase in temperature may increase the brownian motion of the molecules, and the probability of effective collisions between the molecules increases, thereby increasing the reaction rate. However, when the temperature is increased to about 35 ℃, the degradation rate of prometryn is not increased continuously but decreased, and when the test temperature is 25 ℃, the degradation rate of ozone is highest in each treatment time.
Example 5 Effect of pH on the degradation Rate of prometryn
The test method comprises the following steps: fresh Argopecten irradians → soaking in clear water for 72h → soaking in standard prometryn water solution with different concentrations at 0 deg.C for 72h → placing in ozone water under different experimental conditions → removing shell, pulping → extracting, purifying, concentrating → passing through membrane → detecting by gas chromatography.
The test was conducted by selecting five pH ranges of pH 5.0, 6.0, 7.0, 8.0, and 9.0, respectively, and the results are shown in fig. 11, from which it can be obtained that the degradation rate of prometryn by ozone increases with the increase of the pH value of the solution under acidic conditions, whereas the degradation efficiency decreases with the increase of the pH value under alkaline conditions. When the pH is 7.0, the sample treatment time is 30min, and the degradation rate reaches 77.86% at most.
The above disclosure is only for the specific embodiment of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (5)
1. A method for reducing prometryn in marine bivalve shellfish is characterized in that degradation is carried out by utilizing the combined action of direct oxidation of ozone molecules in ozone water and indirect oxidation of active free radicals.
2. The method for reducing prometryn in marine bivalve shellfish of claim 1, comprising the steps of:
1) opening an ozone generator, introducing ozone into the test container at a theoretical yield of 3g/h, receiving ozone by double distilled water, collecting ozone water after 5min of balance, measuring the concentration of ozone in water, and controlling the final concentration of ozone to be 4.0-4.2 mg/L;
2) adding fresh marine bivalve shellfish to be treated;
3) by using Na2CO3Or adjusting the pH value of the solution to 6-7 by citric acid;
4) the temperature of the solution system is 23-27 ℃ in a constant-temperature water bath environment;
5) and cleaning after 20-40 minutes of treatment to obtain the marine bivalve product with greatly reduced prometryn residue.
3. The method for reducing prometryn in marine bivalve shellfish of claim 2, wherein the final concentration of ozone in step 1) is 4.2 mg/L.
4. The method for reducing prometryn in marine bivalve shellfish of claim 2, wherein the temperature in step 4) is 25 ℃.
5. The method for reducing prometryn in marine bivalve shellfish of claim 2, wherein the time for the treatment in step 5) is 30 minutes.
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| JP2005295820A (en) * | 2004-04-07 | 2005-10-27 | Yanmar Co Ltd | Method for purifying bivalve, method for evaluating purification of bivalve, and device for purifying bivalve |
| CN104770626A (en) * | 2015-05-04 | 2015-07-15 | 湖南农业大学 | Method for cleaning fresh fruits and vegetables through aquagenic ozone water |
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|---|---|---|---|---|
| JP2005295820A (en) * | 2004-04-07 | 2005-10-27 | Yanmar Co Ltd | Method for purifying bivalve, method for evaluating purification of bivalve, and device for purifying bivalve |
| CN104770626A (en) * | 2015-05-04 | 2015-07-15 | 湖南农业大学 | Method for cleaning fresh fruits and vegetables through aquagenic ozone water |
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| HANS F.STROO等: "《地下水氯代烃污染羽原位修复》", 31 March 2015, 地质出版社 * |
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