CN114956254A - Method for sterilizing ship ballast water - Google Patents
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- CN114956254A CN114956254A CN202210502986.7A CN202210502986A CN114956254A CN 114956254 A CN114956254 A CN 114956254A CN 202210502986 A CN202210502986 A CN 202210502986A CN 114956254 A CN114956254 A CN 114956254A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/008—Originating from marine vessels, ships and boats, e.g. bilge water or ballast water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for disinfecting ship ballast water, which uses a UV/PDS advanced oxidation method to disinfect and inactivate the ship ballast water containing marine filariasis. The result shows that the UV/PDS technology has high efficiency of inactivating marine coccinella in seawater, and no toxic and harmful substances are generated in the treatment process. The inventor further researches the reaction mechanism of the marine coccid, observes the morphological change of the cells through a field emission scanning electron microscope, and detects the change of the extracellular DNA content and the change of the activity of the antioxidant enzyme in the cells by an enzyme labeling instrument. The results show that significant cell disruption and significant increase in extracellular DNA content after UV/PDS treatment is due to SO 4 ‑ Attack the cell surface, the cell membrane is lysed, resulting in leakage of intracellular DNA out of the cell, which in turn leads to cell death. In summary, the invention has the advantages ofSimple operation, simple equipment, safety, stability, low cost, effective and rapid killing of microorganisms and the like.
Description
Technical Field
The invention belongs to the technical field of water pollution disinfection, and particularly relates to a disinfection method for ship ballast water.
Background
Ocean vessel transport industry is one of the important pillar industries of ocean economy in China, and about 95% of foreign trade in China needs to be completed by ocean shipping. During the sailing process of the ship, the balance and stability are needed to be maintained through the input and output of ballast water. When no cargo is on the ship, ballast water needs to be filled for balancing; ballast water is discharged when the cargo is loaded. This process can result in the spread of organisms from ballast water in different sea areas into the new ecological environment, causing biological invasion. Foreign species invasion has been identified by the global environmental fund organization as one of the four major hazards of the ocean. The ballast water is discharged everywhere, which causes the destruction of the marine ecosystem, poses the threat to the global environment and has potential threat to human activities and health. Therefore, the development of a novel, safe and efficient ship ballast water microbial inactivation technology is an urgent problem to be solved in the long-distance shipping industry.
At present, methods for treating ballast water of ships mainly include mechanical treatment methods (filtration, cyclone separation, etc.), physical treatment methods (ultraviolet rays, ultrasonic waves, heat treatment, etc.), and chemical treatment methods (ozone, hydrogen peroxide, electrolysis, chlorination, etc.). Wherein, the mechanical treatment method and the physical method have high energy consumption and the treatment effect is restricted by various factors; among chemical methods, chlorine-containing disinfectants in common chlorination methods are easy to generate toxic byproducts in the reaction process, thereby harming the environment and human health. Therefore, the safe and effective treatment of ship ballast water has long been one of the research hotspots in the international marine environment.
Based on SO 4 - By generating highly active sulfate radicals (. SO) 4 - ，E 0 1.9-2.8V) to degrade harmful substances in water. The technology has the advantages of strong oxidizability, high oxidation speed and the like, can effectively and quickly kill microorganisms, and does not produce harmful substances and secondary pollution, thereby being widely applied to the field of water body disinfection. SO 4 - By activating monosulfates (HSO) in different ways 5 - PMS and peroxodisulfate (S) 2 O 8 2- PDS), which has the advantages of strong stability, easy storage, low price, etc. compared with PMS. In summary, based on SO 4 - The biological inactivation research of the AOPs in the ship ballast water for protecting the offshore areaThe ecological safety has important scientific significance.
Based on SO 4 - The AOPs have wide research on the field of in-situ remediation and the treatment of the nonbiodegradable organic pollutants. In recent years, the technology is beginning to be applied to the field of water body disinfection, and researches are mainly carried out on the efficiency and mechanism of bacterial inactivation in water bodies such as drinking water, medical wastewater, industrial wastewater and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a ship ballast water disinfection method which is simple to operate, simple in equipment, low in cost, safe, stable, effective and rapid in microorganism killing.
In order to solve the technical problems, the invention adopts the following technical scheme:
application of UV/PDS advanced oxidation method in killing protozoa in seawater is provided.
The protozoa are marine cocculi.
A method for sterilizing ship ballast water comprises sterilizing and inactivating ship ballast water containing marine filariasis (Uronema Marinum) by UV/PDS (Persulfate) advanced oxidation.
The persulfate salt used in the UV/PDS advanced oxidation process is sodium persulfate (Na) 2 S 2 O 8 )。
The initial cell concentration of the marine coccinella is 3000-10000 cells/mL; the initial concentration of the sodium persulfate is 0.01-1 mmol/L; the pH value of the marine product culture water is 5-9; the UV intensity in the UV/PDS advanced oxidation process is 6-25W.
The initial cell concentration of the marine coccinella was 3000 cells/mL.
The initial concentration of sodium persulfate was 1 mmol/L.
The temperature of the ship ballast water is 25 +/-1 ℃, and the pH value is 8.
The UV intensity in the UV/PDS advanced oxidation process was 14W, from a low-pressure mercury lamp with a wavelength of 254 nm.
The sea salt concentration in the ballast water of the ship is 35 per mill.
At present, the methodThe common chemical treatment methods for ship ballast water treatment include ozone, hydrogen peroxide, electrolysis, various chlorine-containing disinfectants and the like, and are limited by high preparation cost, poor treatment effect, environmental friendliness and the like. Therefore, the inventor establishes a disinfection method of the ship ballast water, and uses the UV/PDS advanced oxidation method to disinfect and inactivate the ship ballast water containing the marine filarial worms. In the experiment, the inventor researches the influence of parameters such as different UV intensity, sodium persulfate concentration, cell initial density and pH value on the inactivation efficiency of the marine coccinella. The result shows that the UV/PDS technology has high efficiency of inactivating marine coccinella in seawater, and no toxic and harmful substances are generated in the treatment process. The inventor further researches the reaction mechanism of the marine coccid, observes the morphological change of the cell by a field emission Scanning Electron Microscope (SEM), and detects the change of the extracellular DNA content and the change of the intracellular antioxidant enzyme activity by an enzyme-labeling instrument. The results show that significant cell disruption and significant increase in extracellular DNA content after UV/PDS treatment is due to SO 4 - Attack the cell surface, the cell membrane is lysed, resulting in leakage of intracellular DNA out of the cell, which in turn leads to cell death. In conclusion, the invention has the characteristics of simple operation, simple equipment, safety, stability, low cost, effective and rapid killing of microorganisms and the like.
Previously, the inactivation effect of protozoa in seawater has been rarely reported. The present invention has been primarily explored for this purpose, and is therefore based on SO 4 - The research on the application and mechanism of the AOPs in the ship ballast water is a research with theoretical significance and practical value.
Drawings
FIG. 1 is a graph of the inactivation efficiency of marine filarial worms with different UV intensities in accordance with the present invention.
FIG. 2 is a graph showing the inactivation efficiency of marine cocculid at different sodium persulfate concentrations in the present invention.
FIG. 3 is a graph of the efficiency of inactivation of marine filarial worms by different initial cell densities in the present invention.
FIG. 4 is a graph of the inactivation of marine coccid by different pH values of seawater according to the present invention.
FIG. 5 is a graph of the mechanism of UV/PDS inactivation of marine coccid in the present invention, in which: a: cell scanning electron microscopy; b, DNA content condition; c is superoxide dismutase (SOD); and D, Catalase (CAT) activity.
Detailed Description
Example 1
35g of sea salt (Reef Crystals) was weighed and dissolved in 1L of ultrapure water to prepare 35 ‰ sea water (pH of about 8), and sterilized in a vertical pressure steam sterilizer for 20 min. Adding 10 sterilized and dried wheat grains into 100mL of sterilized seawater, incubating at 37 ℃ for 24h to obtain a wheat grain leachate, taking the wheat grain leachate as a nutrient source, inoculating a proper amount of the marine filaria protection insect body into the wheat grain leachate, and then placing the wheat grain leachate in an incubator at 25 ℃ for culturing for 24h to prepare 3000cells/mL of insect solution.
Example 2
Preparing seawater in the same manner as in example 1, preparing sodium persulfate solution with concentration of 1mmol/L, respectively adjusting UV intensity (wavelength of 254nm low-pressure mercury lamp) to 6W, 14W and 25W, respectively, after UV light intensity is stabilized, transferring 3000cells/mL marine filariasis stock solution prepared respectively to a light-transmitting quartz reaction tube in an aseptic state, putting the light-transmitting quartz reaction tube into a magnetic stirring rotor, respectively adding 200 mu L sodium persulfate solution, putting the quartz reaction tube into a reactor with stable ultraviolet light, taking the reaction tube out for sampling at different reaction time, counting the samples under a biological microscope by using a micro-counting method after sampling, and calculating the inactivation rate of the marine filariasis by UV/PDS under different UV intensities.
As shown in FIG. 1, it was found experimentally that the inactivation rate of marine filarial worms increased from 0.47log to 3.25log at 120s when the ultraviolet light intensity was increased from 6W to 25W. Under the same time, the killing efficiency of the marine coccinella caudada is gradually increased along with the increase of the irradiation intensity of UV. The reason may be that the increased intensity of UV irradiation makes more SO in the UV/PDS system 4 - Is activated, large amount of SO 4 - Attack the microorganisms and ultimately increase the efficiency of inactivation. Thus, it was found that UV light intensity has a greater effect on UV/PDS treatment of microorganisms in seawaterThe better the kill, with increasing UV.
Example 3
Seawater was prepared in the same manner as in example 1, and 0.01mmol/L, 0.10mmol/L and 1mmol/L sodium persulfate solutions were prepared, respectively, and after the UV intensity was fixed at 14W and the low-pressure mercury lamp was stabilized for a while, the remaining reaction steps were the same as in example 2, and the inactivation ratios of marine filarial worms by UV/PDS at different sodium persulfate concentrations were calculated.
As shown in FIG. 2, it was found experimentally that the inactivation rate of marine filarial worms increased from 0.88log to 1.47log when the concentration of sodium persulfate was increased from 0.01mmol/L to 1mmol/L at 120 s. This is because the more sodium persulfate, the more free radicals produced by UV activation, the better the effect of killing microorganisms. Therefore, the higher the sodium persulfate concentration, the better the killing effect within a certain sodium persulfate concentration range.
Example 4
Preparing seawater and 1mmol/L sodium persulfate solution in the same way as in example 1, changing the initial cell density to 3000cells/mL, 5000cells/mL and 10000cells/mL respectively, and calculating the inactivation rate of the Endocarpium maritima at different initial cell densities by using the same reaction steps as in example 2 after the ultraviolet intensity is fixed to 14W and the low-pressure mercury lamp is stabilized for a period of time.
As shown in FIG. 3, it was found experimentally that the initial density of marine coccinella cells increased from 3000cells/mL to 5000cells/mL and 10000cells/mL at 120s, and the inactivation efficiency decreased from 1.47log to 1.39log and 1.12 log. This is due to the higher proportion of active free radicals when the initial density of marine filarial worm cells is lower, providing a greater potential for inactivation of microorganisms. Therefore, the lower the initial density of the biological cells, the better the killing effect of the organisms.
Example 5
Seawater was prepared in the same manner as in example 1, 1mmol/L sodium persulfate solution was prepared, the initial pH values in seawater were adjusted to 5, 6, 7, 8 and 9 by acetic acid and sodium hydroxide, respectively, the reaction procedure was the same as in example 2 after the ultraviolet intensity was fixed at 14W and the low-pressure mercury lamp was turned on and stabilized for a while, and the inactivation ratio of Neurospora maritima at different pH values by UV/PDS was calculated.
As shown in FIG. 4, it was found that at 60s, the initial pH values of the seawater were 5, 6, 7, 8 and 9, and the inactivation efficiencies were 1.18log, 0.96log, 0.85log, 0.78log and 0.44log, respectively, probably due to the SO in the system under acidic and neutral conditions 4 - Predominate, while under alkaline conditions, the system takes OH - Mainly with OH - Comparison,. SO 4 - Has longer half-life, and can increase the contact time of free radicals and microorganisms so as to achieve better inactivation effect. On the other hand, at different pH,. OH - The oxidation potential of (a): OH under acidic conditions - Has an oxidation potential significantly higher than that of OH under alkaline conditions - Oxidation potential of (2). Therefore, under the acidic condition, the killing effect of organisms is better.
Example 6
Preparing seawater in the same manner as in example 1, preparing 1mmol/L sodium persulfate solution, fixing the ultraviolet intensity at 14W, turning on the low-pressure mercury lamp, stabilizing for a period of time, and mixing the 10 prepared solutions 8 Transferring 20mL of marine fiber worm stock solution into a light-transmitting quartz reaction tube (the diameter is 5.0cm, the length is 18cm) under an aseptic condition, putting a magnetic stirring rotor, adding 500 microliter of sodium persulfate solution, putting the quartz reaction tube into a reactor with stable ultraviolet light, taking out the reaction tube at different reaction times for sampling, centrifuging, discarding supernatant, and taking out bottom precipitate. Sterile seawater of about 3 times the volume of the cells was added to wash the cells, centrifuged, and the supernatant was discarded. This was repeated three times. Adding 2.5% fresh glutaraldehyde, suspending and fixing for 24h, washing with sterile seawater for three times, placing into paper bag, performing gradient ethanol dehydration, drying at critical point, lyophilizing at low temperature, and observing cell morphology by projection scanning electron microscope.
As shown in A in FIG. 5, the untreated marine coccyx cells were found to be smooth in surface and intact in morphology. Slight wrinkles and pits appeared on the cell surface after UV irradiation, and significant cell disruption occurred after UV/PDS treatment.
Example 7
Seawater was prepared in the same manner as in example 1, and a 1mmol/L sodium persulfate solution was prepared, which was then irradiated under UV irradiationThe temperature is fixed to be 14W, after the low-pressure mercury lamp is switched on and stabilized for a period of time, 10 prepared respectively 8 Transferring 50mL of marine coccyx stock solution into a light-transmitting quartz reaction tube in a sterile state, putting a magnetic stirring rotor, adding 500 mu L of sodium persulfate solution, putting the quartz reaction tube into a reactor with stable ultraviolet light, taking out the reaction tube for sampling at different reaction times, centrifuging, taking supernatant, measuring absorbance under a microplate reader, and calculating the DNA content.
As shown in FIG. 5B, it was found that the extracellular DNA content was slightly increased after UV irradiation, and significantly increased after UV/PDS treatment, indicating that damage to the cell membrane resulted in leakage of intracellular DNA outside the cell.
Example 8
Preparing seawater in the same manner as in example 1, preparing 1mmol/L sodium persulfate solution, fixing the ultraviolet intensity at 14W, turning on the low-pressure mercury lamp, stabilizing for a period of time, and mixing the 10 prepared solutions 8 Transferring 50mL of marine coccyx stock solution into a light-transmitting quartz reaction tube in a cell/mL sterile state, adding a magnetic stone, adding 500 mu L of sodium persulfate solution, putting the quartz reaction tube into a reactor with stable ultraviolet light, taking out the reaction tube for sampling at different reaction times, centrifuging at 8000r/min for 10min, discarding the supernatant, washing with sterile seawater for three times, collecting cell precipitates, and then cracking with a cell crusher. And (3) sequentially adding corresponding reagents according to the specifications of the BCA protein extraction kit, the total SOD determination kit and the CAT determination kit, dripping the prepared liquid to be detected into a 96-well plate, and determining the absorbances of the protein, the SOD and the CAT in 562, 560 and 405nm respectively by using a multifunctional microplate reader.
As shown in FIGS. 5C and D, no significant change in cellular enzyme activity was observed under PDS treatment. The activity change of the enzyme in the UV/PDS system is severe compared with that of a single UV system, and the activities of SOD and CAT sharply increase along with the increase of time within the first 120s of the reaction, so that a large amount of oxides in the system attack the marine filaria, and the oxidative stress system shows that the activities of SOD and CAT are increased to ensure the activity of the marine filaria. Thereafter, the expression of both SOD and CAT enzyme activities gradually decreased, indicating that a large number of oxidative species have exceeded the load of the marine coccid stress system, destroying its defense functions.
Claims (10)
- The application of UV/PDS advanced oxidation method in killing protozoa in sea water.
- 2. Use according to claim 1, characterized in that: the protozoa are marine cocculi.
- 3. A method for sterilizing ship ballast water is characterized in that the ship ballast water containing marine filariasis is sterilized and inactivated by using a UV/PDS advanced oxidation method.
- 4. The method of sterilizing ship ballast water according to claim 1, wherein: the persulfate used in the UV/PDS advanced oxidation process is sodium persulfate.
- 5. The disinfection method of ship ballast water according to claim 3, wherein: the initial cell concentration of the ocean filarial worms is 3000-10000 cells/mL; the initial concentration of the sodium persulfate is 0.01-1 mmol/L; the pH value of the marine aquaculture water is 5-9; the UV intensity in the UV/PDS advanced oxidation process is 6-25W.
- 6. The disinfection method of ship ballast water according to claim 5, wherein: the initial cell concentration of the marine filaria is 3000 cells/mL.
- 7. The disinfection method of ship ballast water according to claim 5, wherein: the initial concentration of the sodium persulfate was 1 mmol/L.
- 8. The disinfection method of ship ballast water according to claim 5, wherein: the temperature of the ship ballast water is 25 +/-1 ℃, and the pH value is 8.
- 9. The disinfection method of ship ballast water according to claim 5, wherein: the UV intensity in the UV/PDS advanced oxidation process was 14W, from a low pressure mercury lamp with a wavelength of 254 nm.
- 10. The disinfection method of ship ballast water according to claim 5, wherein: the sea salt concentration in the ship ballast water is 35 per mill.
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| US20070193958A1 (en) * | 2005-06-22 | 2007-08-23 | Truox, Inc. | Composition and method for enhanced sanitation and oxidation of aqueous systems |
| CN101045573A (en) * | 2007-03-16 | 2007-10-03 | 大连海事大学 | Method for treating ship ballast by high-level oxidation technology based on sulphuric acid free radical |
| CN105036291A (en) * | 2015-08-05 | 2015-11-11 | 同济大学 | Method for degrading smelly substance in water through oxidizing agent activated by ultraviolet light |
| CN112939164A (en) * | 2021-03-15 | 2021-06-11 | 广西大学 | Novel disinfection method for marine aquaculture water body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070193958A1 (en) * | 2005-06-22 | 2007-08-23 | Truox, Inc. | Composition and method for enhanced sanitation and oxidation of aqueous systems |
| CN101045573A (en) * | 2007-03-16 | 2007-10-03 | 大连海事大学 | Method for treating ship ballast by high-level oxidation technology based on sulphuric acid free radical |
| CN105036291A (en) * | 2015-08-05 | 2015-11-11 | 同济大学 | Method for degrading smelly substance in water through oxidizing agent activated by ultraviolet light |
| CN112939164A (en) * | 2021-03-15 | 2021-06-11 | 广西大学 | Novel disinfection method for marine aquaculture water body |
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