CN116986652A - Method for treating polluted water body by using water quality regulator - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 33
- 241000195493 Cryptophyta Species 0.000 claims abstract description 104
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 84
- 230000000694 effects Effects 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 26
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 241000196294 Spirogyra Species 0.000 claims abstract description 8
- 241000195628 Chlorophyta Species 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 241000192700 Cyanobacteria Species 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 241000192542 Anabaena Species 0.000 claims description 4
- 241000192701 Microcystis Species 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 241000192707 Synechococcus Species 0.000 claims 2
- 239000000356 contaminant Substances 0.000 claims 2
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- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 239000003619 algicide Substances 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 12
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- 229930002868 chlorophyll a Natural products 0.000 description 12
- 241000192710 Microcystis aeruginosa Species 0.000 description 10
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000005708 Sodium hypochlorite Substances 0.000 description 7
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004155 Chlorine dioxide Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 235000019398 chlorine dioxide Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000002353 algacidal effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229940043430 calcium compound Drugs 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
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- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
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- 241000251468 Actinopterygii Species 0.000 description 2
- 102000000412 Annexin Human genes 0.000 description 2
- 108050008874 Annexin Proteins 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 241000192560 Synechococcus sp. Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019804 chlorophyll Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001784 detoxification Methods 0.000 description 2
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- 241000223600 Alternaria Species 0.000 description 1
- 241000192531 Anabaena sp. Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000980781 Cladosiphon Species 0.000 description 1
- 241000219764 Dolichos Species 0.000 description 1
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- 235000006439 Lemna minor Nutrition 0.000 description 1
- 241001183453 Longispora Species 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241000192709 Microcystis sp. Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001560086 Pachyrhizus Species 0.000 description 1
- 241000317981 Podosphaera fuliginea Species 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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- 239000012148 binding buffer Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
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- 229930002875 chlorophyll Natural products 0.000 description 1
- 210000003763 chloroplast Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 235000021472 generally recognized as safe Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a method for treating polluted water by utilizing a water quality regulator, wherein the water quality regulator comprises acidic calcium sulfate; the pollutants in the polluted water body comprise blue algae, green algae, moss or spirogyra. The safety of the acid calcium sulfate is high, and the algae removal effect can be seen after half an hour under the use dilution ratio of three thousandths. After one hour, blue algae subside obviously and die, which is obviously superior to the existing common chemical algicides on the market; no secondary pollution, no corrosiveness and low cost. Can be widely used and is convenient to apply. The method is very suitable for emergency treatment and control of blue algae outbreak.
Description
Field of the art
The invention relates to a method for treating a polluted water body, in particular to a method for treating the polluted water body by using a water quality regulator named as acid calcium sulfate.
(II) background art
Lake eutrophication and cyanobacterial bloom occurrence are one of the significant environmental problems commonly faced worldwide at present. Cyanobacterial bloom is a natural ecological phenomenon of excessive rapid proliferation of cyanobacterial algae caused by water eutrophication, and is also a secondary pollution, and the appearance is characterized in that algae aggregates or algae particles are suspended in the water body on the surface of the water body. In the context of global warming, algae bloom is increasingly frequent as human activity increasingly affects the surrounding environment.
The outbreak of cyanobacteria bloom has great damage to an aquatic ecological system, can also cause a plurality of problems such as environmental pollution, water quality safety and the like, and has adverse effects on fishery, industry, agriculture, travel industry, daily life and the like. Blue algae bloom can release peculiar smell and algae toxin, and the death of aquatic animals such as fish and the like is caused. After the algae die, the algae decompose to make the water body blacken and smelly.
Currently, conventional algae removal methods mainly comprise technologies in chemical, physical, biological aspects and the like. The chemical algicide is used as an oxidizing agent (hydrogen peroxide, ozone, chlorine dioxide, sodium hypochlorite, potassium hydrogen persulfate, etc.), an algicide (copper sulfate, isothiazolinone, etc.), an antibiotic, etc., to kill algae cells directly. The existing chemical algicide can reduce the concentration of algae in water in a short time, and has the characteristics of simple operation, obvious effect and the like. However, the existing chemical algicide has low safety and large dosage, can cause damage to microorganisms, animals and plants in water, and is easy to cause secondary pollution. In addition, algae are prone to developing resistance when certain algicides are administered for a long period of time. Copper ions can destroy intracellular material such as chloroplasts, resulting in a reduction or death of algal cell organisms. However, the metal ions have certain toxicity, and the excessive addition amount easily causes the concentration of copper ions in the water body to exceed the biosafety guard line, thereby damaging the ecological system of the water body. Chlorine dioxide is used as a novel algaecide, and the effect is better than Cl 2 More efficient but still produce Cl - And the risk of exceeding the standard, and the substances have potential toxicity to mammals.
In summary, the prior market lacks the algae removal technology and product with safety, high efficiency, quick effect, wide use range, convenience and no secondary pollution, so the development of the novel algae removal agent with high efficiency, safety, environmental protection and no secondary pollution, which can be widely used, is urgent.
Acidic calcium sulfate (Acidic Calcium Sulflate, ACS for short) is an acidic or low pH solution of a novel sparingly-soluble group iia complex (AGIIS) developed by the company Miaoniss, U.S. Pat. No. 3, 25348299, CN100490684C, and the main applications include: cleaning, food production, disinfection, biological decontamination, agricultural applications, medical applications, detoxification of substances, and the like. ACS is a recognized safety component (Generally Recognized as Safe, abbreviated as GRAS) with a strong bactericidal effect.
However, research and application of ACS in the treatment of blue algae and other polluted water bodies have not been found and reported yet. The invention aims to provide a new scheme for treating polluted water bodies containing blue algae and the like.
(III) summary of the invention
The invention aims to provide a method for treating a polluted water body by using a water quality regulator, which solves the problems that the existing cyanobacteria bloom control technology has low efficiency, poor safety and no effective method for treating high-concentration cyanobacteria with sudden burst.
The technical scheme adopted by the invention is as follows:
the invention provides a method for treating a polluted water body by using a water quality regulator, wherein the water quality regulator comprises Acid Calcium Sulfate (ACS), and pollutants in the polluted water body comprise blue algae, green algae, moss or spirogyra.
Preferably, the method is to add a water quality regulator into the polluted water body to eliminate pollutants.
Preferably, the cyanobacteria include algae commonly used in polluted water bodies such as Microcystis (Microcystis sp.), anabaena (Anabaena sp.), aphanomannia sp., aphanomannia longifolia (Dolichos sp.), synechococcus sp., planktophyta sp., pachyrhizus sp., planktophythrix sp., padorina sp., euglena sp., aureopsis sp., fragile sp., nepalustria sp., scenemia sp., or Cladosiphon sp., etc.
Preferably, the addition amount of the water quality regulator (especially acid calcium sulfate with the equivalent concentration of 16.0N) and the volume ratio (V: V) of the polluted water body are 1:100-1000000, and the use concentration under different conditions is related to the degree of pollutants such as cyanobacteria bloom, moss, spirogyra and the like which need to be controlled.
Preferably, when the density of blue algae cells in the polluted water body to be treated is less than or equal to 1.0X10 based on the inhibition rate of more than or equal to 50 percent 3 cells·mL -1 When the ACS is applied, the volume ratio of the ACS to the water body (V: V) =1:100000 is one ten thousandth;
when the density of blue algae cells in the polluted water body to be treated is 1.01X10 3 ～1.0×10 5 cells·mL -1 When the ACS is applied, the volume ratio of ACS to water (V: V) =1:10000;
when the density of blue algae cells in the polluted water body to be treated is 1.01X10 5 ～1.0×10 7 cells·mL -1 When the ACS is applied, the volume ratio of the ACS to the water body (V: V) =1:3000 is three thousandths;
when the density of blue algae cells in the water body to be treated is more than or equal to 1.01X10 7 cells·mL -1 When the ACS is applied, the volume ratio of ACS to water body (V: V) =1 (100-2000) is two thousandths.
Preferably, the water quality regulator of the present invention further comprises a mixture of one or more of the following auxiliaries: organic acid, inorganic acid, organic alcohol, and oxidizing agent; the organic acid comprises acetic acid; the organic alcohol comprises ethanol and the oxidizing agent comprises hydrogen peroxide.
The ACS is prepared by mixing calcium hydroxide, calcium sulfate, sulfuric acid and water as raw materials, wherein the concentration of the ACS is more than 0.1N; the ACS is added into a water body containing blue algae to be treated, and can be preferentially added into a key area with dense blue algae and high local concentration; the water area to be treated and the cyanobacteria bloom comprise compound harmful organisms except common algae, such as filamentous algae like spirogyra and other aquatic pollutants like moss; the ACS application volume ratio can be properly adjusted according to different seasons, water temperatures, algae growth vigor and the like, and the use frequency is increased or the concentration is increased under the serious conditions such as burst and the like; the ACS can be used independently, can be combined with organic acid, inorganic acid, ethanol, hydrogen peroxide and the like, and can also be used together with other physical algae control and removal measures; the measurement of the density and severity of algae to be treated by the cyanobacteria can also be performed according to the volume concentration of algae (for example, the volume concentration of algae in water is 100 milliliters/liter), chlorophyll concentration (for example, 5000 micrograms/liter), algae cell density and the like.
Preferably, the acidic calcium sulfate is prepared as follows: dropwise adding sulfuric acid into a reaction kettle filled with deionized water, stirring, slowly adding calcium sulfate, and cooling to 8-12 ℃; mixing a calcium compound with deionized water, stirring, adding the mixture into a reaction kettle in batches, controlling the temperature to be 8-12 ℃, and adding the mixture completely; continuing to keep the temperature and stir for 3-6h (preferably 4 h); discharging and filtering to obtain acidic calcium sulfate; the sulfuric acid is preferably 98% concentrated sulfuric acid; the calcium compound is calcium hydroxide, calcium oxide, calcium carbonate or calcium bicarbonate, more preferably calcium hydroxide; the feeding mass ratio of the calcium sulfate to the concentrated sulfuric acid is 1:200-210, and the feeding mass ratio of the calcium compound to the concentrated sulfuric acid is (0.075-0.75): 1, a step of; the total volume of deionized water is 120-150L/Kg based on the mass of calcium sulfate.
Compared with the prior art, the invention has the beneficial effects that:
1. the ACS has high safety. ACS is promulgated by the united states Food and Drug Administration (FDA) as a "generally recognized safe use substance (GRAS)", and the determination of "GRAS" is a decision made by the food industry in accordance with relevant legal regulations, published scientific evidence or history of long-term use, and its judicious assessment of safety under specific conditions of use. Therefore, the safety of the material can be absolutely ensured, and the material is widely applied to the fields of cleaning, food production, disinfection, biological decontamination, agricultural application, medical application, detoxification of the material and the like. This is currently not an advantage of any other chemical algaecide;
2. high efficiency. The application volume ratio of ACS is three thousandths, namely when ACS is in water body (V: V) =1:3000), the algae removal effect can be observed after 0.5 h. After 1h, obvious sedimentation and death of blue algae are observed. The high efficiency of ACS is also reflected in effectively treating high-concentration cyanobacterial bloom, which is obviously superior to the conventional chemical algicides on the market at present;
3. no secondary pollution and no corrosiveness. ACS belongs to a highly structured complex inorganic acid, the original structure of which disintegrates after algae removal, and algae mud formed by the ACS and the inactivated blue algae is sunk into the water bottom;
4. the cost is low. The ACS is widely available in raw material source, low in cost and easy to obtain, the preparation process is simple, and the manufacturing cost is low;
5. can be widely used and is convenient to apply. The method is very suitable for emergency treatment and control of blue algae outbreak.
(IV) description of the drawings
FIG. 1 is a graph of alkali to acid ratio versus acid calcium sulfate equivalent concentration.
FIG. 2 is a graph showing the effect of time of change of chlorophyll a concentration in microcystis aeruginosa under the action of acid calcium sulfate with different concentrations.
FIG. 3 is a graph showing the effect of the change time of the percentage of intact cells of microcystis aeruginosa under the action of acid calcium sulfate with different concentrations.
FIG. 4 is a graph showing the effect of the turbidity change time of microcystis aeruginosa under the action of acid calcium sulfate with different concentrations.
Fig. 5, and the comparative photographs of the Acid Calcium Sulfate (ACS) treated blue algae before and after treatment in example 4, A, B are untreated controls, and C is a treatment group.
FIG. 6 is a photomicrograph of the Acid Calcium Sulfate (ACS) treated blue algae of example 4 before and after treatment; a: untreated cyanobacteria cells, intact. B: cells after ACS treatment for 1h, ruptured and dead.
FIG. 7, comparative photographs of the algicidal effect of the different algicides in example 4, 1-1 chlorine dioxide, 2-1 hydrogen peroxide, 3-1 potassium hydrogen persulfate, 4-1ACS,5-1 sodium hypochlorite (containing 5.2% active chlorine).
FIG. 8 is a photograph of a blue algae outbreak pond treated with Acidic Calcium Sulfate (ACS).
(fifth) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto: the room temperature of the invention is 22-25 ℃.
Examples 1, 16.0N Acid Calcium Sulfate (ACS) preparation
1050Kg of 98% strength concentrated sulfuric acid was added dropwise to a 2000 liter reaction vessel containing 380Kg of deionized water, stirred, slowly charged with 5Kg of calcium sulfate, and cooled to 8 ℃. 182Kg of calcium hydroxide powder (food grade, purity over 98%) and 260Kg of deionized water are mixed, stirred, added into a reaction kettle in batches, and the temperature is controlled between 8 ℃ and 12 ℃ after the addition. And continuing to keep the temperature and stir for 4 hours. Discharging, filtering, and collecting filtrate to obtain 16.0N acid calcium sulfate (ACS for short).
The amount ratio of the substances of the calcium hydroxide and the concentrated sulfuric acid (namely, different alkali-acid ratios) is adjusted to obtain Acid Calcium Sulfate (ACS) with different equivalent concentrations, and the acid calcium sulfate with the required equivalent concentration can be formed by dilution with deionized water as shown in figure 1.
EXAMPLE 2 algicidal Effect of acidic calcium sulfate on Microcystis aeruginosa
1. Experimental materials
The experimental algae is microcystis aeruginosa (Microcystis aeruginosa) from the aquatic organism germplasm library of China academy of sciences of China.
2. Experimental method
Into a 1L flask was placed 300mL of BG11 medium (Gibco TM BG-11 Media), inoculating microcystis aeruginosa to a concentration of 1 x 10 7 cells·mL -1 And 1.3 x 10 7 cells·mL -1 As microcystis aeruginosa liquid. 150mL of microcystis aeruginosa liquid is taken and added into a 250mL cell culture flask, and then 16.0N acid calcium sulfate prepared in the method of example 1 is added according to the amount of 0, 0.2, 0.3 and 0.5mL/L, and the continuous observation is carried out for 168 hours at room temperature. Obtaining algae liquid treated by different amounts of acidic calcium sulfate, and taking the algae liquid for sample analysis.
3. Sample analysis
(1) Chlorophyll a (chlorophyl a, chl-a) concentration was measured using a four-band assay: taking 5mL of algae liquid, carrying out suction filtration by using a GF/C glass fiber filter membrane (Whatman, diameter 47mm and aperture 1.2 mu m), soaking a filter cake after suction filtration and the filter membrane in 8mL of 90% ethanol water solution with volume concentration, standing at room temperature and dark condition for 24h, centrifuging at 3500rpm for 15min, carefully sucking the supernatant, and measuring absorbance values of the supernatant at 750, 663, 645 and 630nm, wherein the sample is prevented from shaking severely in the whole extraction and measurement process. The concentration of chlorophyll a is measured according to the four-band measuring method of the national environmental protection standard Spectrophotometry (HJ 897-2017) of chlorophyll a of water quality, the result is shown in figure 2, and figure 2 shows that after ACS treatment for 72 hours with the concentration of chlorophyll a of 0.5mL/L, the concentration of chlorophyll a is reduced to about 0.26mg/L, and the algae removal effect is remarkable.
(2) Algal cell integrity: the combination of flow cytometry with fluorescent molecular probes provides an opportunity to assess microbial cell membrane integrity.
The algae liquid is taken 5ml,1000 Xg (about 1000-2000 rpm) is centrifuged for 5 minutes, the supernatant is discarded, the cells are collected, the cells are lightly resuspended and counted by PBS, and the effect of washing the cells is also achieved when the PBS is resuspended.
Taking 5-10 ten thousand resuspended cells, centrifuging for 5 minutes at 1000 Xg, discarding the supernatant, detecting the sediment by using an apoptosis detection kit (SYTOX Green, biyun days), adding 194 mu L of Annexin V-mCherry Binding Buffer light and light resuspended cells, adding 5 mu L of Annexin V-mCherry and 1 mu L of SYTOX Green, and gently mixing. Incubation for 10-20 min at room temperature (20-25 ℃) in the absence of light, followed by placing in an ice bath. Light protection can be performed with aluminum foil. The incubation process may be repeated 2-3 times to improve the labelling effect. The ratio of cellular activities was then measured by flow cytometry. The results are shown in FIG. 3, and FIG. 3 shows that after 12 hours of ACS treatment at 0.3mL/L, the percentage of intact cells was reduced to 0.606%; after ACS treatment for 12 hours at 0.5mL/L, the percentage of intact cells is reduced to 0.316 percent, the cell death rate is over 99 percent, and the algae removal effect is remarkable.
(3) Measurement of turbidity: a turbidity meter (hash 2100Q is portable) is adopted, and after the machine is started and preheated for 30 minutes, a calibration/measurement toggle switch is arranged at a measurement position; the appropriate range is selected by pressing the "key head" key. (to reduce errors, a low range is selected but cannot be exceeded); slowly injecting 10mL of algae liquid to be detected, and wiping the sample cup with filter paper; and stably placing the sample cup into a colorimetric pool, covering an inner cover of the colorimetric pool, closing the cover of the colorimetric pool, and reading the turbidity value of the measured solution after the display data are stable. In the process of measuring the sample, if the measured sample is not in the same measuring range, the measuring range is switched by pressing a measuring range key. (in addition, in order to ensure good measurement repeatability, the wide positioning strip of the sample cup is required to face the user). The results are shown in FIG. 4, and FIG. 4 shows that turbidity was reduced by more than 95% after 12h of ACS treatment at 0.3 mL/L.
EXAMPLE 3 inhibition of several common aquatic algae by acid calcium sulfate
The inhibition effect of ACS (16.0N) in example 2 was changed to 0.3mL/L by the method of example 2, and after 12. 12h treatment, the inhibition effect of ACS on several other common aquatic algae except for microcystis aeruginosa was examined, and the results were evaluated and compared using chlorophyll a concentration change, whole cell percentage and turbidity as indexes, and are shown in table 1.
TABLE 1 results of treatment of several algae with acidic calcium sulfate
| Algae species | Chlorophyll a concentration decrease rate | Percentage of intact cells | Turbidity reduction (%) |
| Microcystis (Microcystis) | 67.3％ | 0％ | 96.4％ |
| Anabaena (Anabaena) | 71.5％ | 0％ | 98.3％ |
| Sphaerotheca fuliginea (L.) Kuntze | 70.2％ | 0％ | 97.5％ |
| Alternaria longispora | 69.6％ | 0％ | 96.8％ |
| Synechococcus sp | 68.3％ | 0％ | 97.5％ |
| Water cotton | 70.6％ | 0％ | 97.2％ |
Experimental results show that ACS has remarkable effect of killing the tested algae cells, the concentration of chlorophyll a is obviously reduced, and the turbidity removal rate is high.
Example 4 comparison of the effects of different algicides
1. ACS algae removal effect
200mL of algae water from a pond with blue algae eruption under natural conditions in the Shore region of Hangzhou, zhejiang province is added with 16.0N acid calcium sulfate prepared by the method of example 1 according to the volume ratio of 1:2000, the algae settling occurs after the water is left for 1h at room temperature, and the algae settling is basically complete after 4h (figure 5). Blue algae cells were found to rupture and die by microscopic observation before and after ACS treatment for 1h (fig. 6).
2. Comparison of the algae removal effect of ACS with several commonly used chemical algae removal agents
(1) Observation of algae removal effect of five algae removal agents
2L of algae water from a pond with blue algae eruption under natural conditions in Xiaoshan region of Hangzhou, zhejiang province is added with 0.2mL of 16.0N acid calcium sulfate prepared by the method of example 1, and the photo after being left at room temperature for 4 hours is shown as 4-1 in FIG. 7.
Under the same conditions, ACS was replaced with an equal volume of chlorine dioxide (2%, liquid), hydrogen peroxide (30%), potassium hydrogen persulfate (0.1 g was added to 10mL of water to prepare a solution), sodium hypochlorite (containing 5.2% active chlorine), and the volume ratio of each algaecide to the amount of algae water was 1:10000 (V: V). The results are shown in FIG. 7, wherein 1-1,2-1, 3-1,4-1,5-1 are chlorine dioxide, hydrogen peroxide, potassium hydrogen persulfate, acid calcium sulfate, sodium hypochlorite (containing 5.2% active chlorine), respectively.
As a result, it was found that the effect of the acid calcium sulfate treatment was most remarkable after 4 hours of treatment, the algae was sedimented and ruptured, and the chlorophyll a content was reduced.
(2) Determination of algae removal Effect
The algae removal effect of several algae removal agents, namely 16.0N acid calcium sulfate, copper sulfate (solid), potassium hydrogen persulfate (solid), hydrogen peroxide (30%) and sodium hypochlorite solution (containing 5.2% of active chlorine) prepared in the method of example 1, was measured by taking 300mL of algae water from a pond with blue algae eruption under natural conditions in the Shoshan region of Hangzhou city of Zhejiang province. Each algaecide provided a concentration gradient, ACS: 0. 0.2, 0.3, 0.5mL/L (16.0N ACS volume/algae volume); copper sulfate: 0. 1.5, 3, 5mg/L; potassium hydrogen persulfate: 0. 61.55, 123.1, 246.2mg/L; hydrogen peroxide: 0. 10.2, 51 and 102mg/L; sodium hypochlorite (5.2% active chlorine): 0.2, 3 and 4mg/L. Each algaecide concentration was set in 3 replicates and samples were taken in each concentration gradient to measure their cell integrity, chlorophyll a concentration and turbidity change. Sampling times were set to 0, 0.1, 0.5, 1, 12, 24, 48, 72, 168h. The results in Table 2 show that the effect of ACS disruption of cells was significant at 1h 0.5 mL/L. At ACS concentrations of 0.3mL/L and 0.2mL/L, chlorophyll a concentration in the sample decreased significantly with increasing contact time with algaecide, turbidity decreased by more than 90%, and no intact cells were found under microscopic observation. The optimal dosage of ACS algae removal is 0.2mL/L, the optimal algae removal dosage of copper sulfate is 1.5mg/L, the optimal algae removal concentration of potassium hydrogen persulfate is 123.1mg/L, the optimal algae removal dosage of hydrogen peroxide algae removal is 51mg/L, and the optimal algae removal dosage of sodium hypochlorite solution (containing active chlorine 5.2%) is 3.0mg/L. ACS effect was best from comprehensive analysis of reaction rate and algae control effect (Table 2).
TABLE 2 comparison of the comprehensive algicidal effects of several algicides
Example 5 blue algae treatment in high concentration blue algae outbreak pond
Pond (about 1500m in area) of red mountain village in Xiaoshan region of Hangzhou city in Zhejiang province 2 Water depth of about 2 m) blue algae bloom pollution occurs annually in recent years. The blue algae in the pond can be developed early, the blue algae in summer and autumn can be exploded seriously, the density of the blue algae floating on the water surface is high, and the fishy smell can be diffused. ACS treatment is respectively carried out twice in 2020 and 2021, and obvious algae control and removal effects are obtained.
In the year 2020, 11 months, when the blue algae in the pond is exploded, 12.0N ACS is sprayed on the water surface of the blue algae in the pond, after 1L of ACS is used for 1 week, the blue algae basically disappear, and the water surface becomes clear, as shown in figure 8.
The blue algae in the pond burst in a large area and has serious degree in 2021 and 7 months. The ACS was used for treatment, and the 16.0N ACS prepared in the method of example 1 was sprayed on the water surface, so that the dosage of the important area was increased, and the total dosage of ACS was 20Kg. After 10 days of treatment, blue algae are controlled, the amount of blue algae floating on the water surface is obviously reduced, the blue algae gradually disappear after 14 days, the water surface becomes clear, duckweed which is other beneficial aquatic organisms on the water surface begins to appear, and swimming fishes are easy to see.
Example 6 treatment of Water bodies in which the spirogyra occur
In 2021, natural water in Huangshan city, anhui province was contaminated with water cotton (belonging to the family of algae of the family of the biseriaceae). The 16.0N ACS prepared in example 1 was treated with a proportion of ten thousandth of the volume of the water, and after three days the spirogyra disappeared and the green color disappeared. The spirogyra are easy to float on the water surface when encountering high temperature and sunlight, and basically do not float after ACS treatment.
Claims (10)
1. A method for treating a contaminated water body with a water quality regulator, wherein the water quality regulator comprises acidic calcium sulfate.
2. The method of claim 1, wherein the contaminants in the contaminated water body comprise blue algae, green algae, moss, or spirogyra.
3. The method of claim 1, wherein the cyanobacteria comprises microcystis, anabaena, synechococcus, ascophyceae, spirochete, float silk, synechococcus, euglena, dinoflagellate, hydrotheca, or cladophora.
4. The method of claim 1 wherein said water quality regulator is added to the body of contaminated water to be treated to effect the elimination of contaminants.
5. The method of claim 4, wherein the acidic calcium sulfate is added in an amount of 1:100-1000000 by volume of the contaminated water.
6. The method of claim 4, wherein the blue algae cell density in the contaminated water to be treated is 1.0X10 or less 3 cells·mL -1 When the volume ratio of the acidic calcium sulfate to the polluted water body is 1:100000.
7. The method of claim 4, wherein the blue algae cell density in the contaminated water to be treated is 1.01X10 3 ～1.0×10 5 cells·mL -1 When the acid calcium sulfate and the polluted water body are in a volume ratio of 1:10000.
8. The method according to claim 4, wherein the method comprises,it is characterized in that when the density of blue algae cells in the water body to be treated is 1.01X10 5 ～1.0×10 7 cells·mL -1 When the acid calcium sulfate and the polluted water body are in a volume ratio of 1:3000.
9. The method according to claim 4, wherein when the density of blue algae cells in the polluted water body to be treated is not less than 1.01X10 7 cells·mL -1 When the acid calcium sulfate and the polluted water body are in a volume ratio of 1:2000.
10. The method of claim 1, wherein the acidic calcium sulfate is prepared by mixing calcium hydroxide, calcium sulfate, concentrated sulfuric acid and water as raw materials to form a solution with a concentration of more than 0.1N.
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