CN115340875B - Barrier agent for reducing content of harmful heavy metals in plants, use method and application - Google Patents
Barrier agent for reducing content of harmful heavy metals in plants, use method and application Download PDFInfo
- Publication number
- CN115340875B CN115340875B CN202211041772.0A CN202211041772A CN115340875B CN 115340875 B CN115340875 B CN 115340875B CN 202211041772 A CN202211041772 A CN 202211041772A CN 115340875 B CN115340875 B CN 115340875B
- Authority
- CN
- China
- Prior art keywords
- soil
- agent
- heavy metals
- content
- barrier agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 95
- 239000012754 barrier agent Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005507 spraying Methods 0.000 claims abstract description 49
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 9
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 claims abstract description 9
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 claims abstract description 9
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims abstract description 9
- 229950006780 n-acetylglucosamine Drugs 0.000 claims abstract description 9
- 239000002689 soil Substances 0.000 claims description 77
- 239000002981 blocking agent Substances 0.000 claims description 52
- 241000196324 Embryophyta Species 0.000 claims description 32
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- 239000003337 fertilizer Substances 0.000 claims description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003971 tillage Methods 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical group OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 241000209094 Oryza Species 0.000 description 12
- 235000007164 Oryza sativa Nutrition 0.000 description 12
- 241001122767 Theaceae Species 0.000 description 12
- 235000009566 rice Nutrition 0.000 description 12
- 238000001514 detection method Methods 0.000 description 9
- 238000005070 sampling Methods 0.000 description 8
- 235000007650 Aralia spinosa Nutrition 0.000 description 7
- 241000949456 Zanthoxylum Species 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 235000002566 Capsicum Nutrition 0.000 description 6
- 239000006002 Pepper Substances 0.000 description 6
- 241000722363 Piper Species 0.000 description 6
- 235000016761 Piper aduncum Nutrition 0.000 description 6
- 235000017804 Piper guineense Nutrition 0.000 description 6
- 235000008184 Piper nigrum Nutrition 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000012795 verification Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000003306 harvesting Methods 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000004720 fertilization Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000003973 irrigation Methods 0.000 description 3
- 230000002262 irrigation Effects 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003895 organic fertilizer Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000003900 soil pollution Methods 0.000 description 3
- 235000009024 Ceanothus sanguineus Nutrition 0.000 description 2
- 240000003553 Leptospermum scoparium Species 0.000 description 2
- 235000015459 Lycium barbarum Nutrition 0.000 description 2
- 244000089698 Zanthoxylum simulans Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 210000002768 hair cell Anatomy 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003621 irrigation water Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000013441 quality evaluation Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000002688 soil aggregate Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Mycology (AREA)
- Microbiology (AREA)
- General Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Botany (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a barrier agent for reducing the content of harmful heavy metals in plants, which comprises soluble phosphate, quaternized chitosan and N-acetylglucosamine, and also provides a use method and application of the barrier agent. The ecological chemistry combined restoration technology is used for heavy metal blocking, secondary pollution is not introduced, and the content of harmful heavy metals in plants can be obviously reduced under the condition of low-concentration spraying.
Description
Technical Field
The invention belongs to the technical field of farmland restoration of heavy metal pollution, and particularly relates to a blocking agent for reducing the content of harmful heavy metals in plants, a use method and application thereof.
Background
Investigation of the soil pollution condition of the whole country shows that the soil environment of the country is not optimistic, the soil pollution of partial areas is heavy, and the soil environment quality of cultivated lands is candid. Heavy metal pollution area of the cultivated land in China exceeds 16%, wherein the situation is quite serious around large cities and mining areas, and serious hidden danger is brought to water environment and food safety. According to measurement and calculation, the current grain polluted by heavy metal is up to 1200 ten thousand tons each year, which is equivalent to 4000 ten thousand people grains for one year. The heavy metal pollution has the characteristics of wide range, long-term property, enrichment, long-term property, high toxicity and the like, and the enrichment is generated through long-term intake of food chains, so that the human health is seriously threatened. Heavy metals not only have negative effects on the quantity, population structure and soil enzyme activity of soil microorganisms, so that the soil fertility is reduced, but also interfere with the normal growth metabolism of crops, reduce the yield and quality of crops, finally accumulate in human bodies through food chains, cause harm to the health of the human bodies, seriously affect the prevention and health care effects of functional nutritional agricultural products, and become bottleneck constraints of functional agricultural development.
In 2016, china promulgates a soil pollution control action plan, determines the thought of agricultural land classification management, and is safe for medium and light pollution farmlands. The national agricultural rural department in 2019 issues 'guide rules for treatment and repair of polluted cultivated land', proposes a selection treatment and repair mode according to local conditions, reduces the input and total amount of pollutants in the cultivated land soil or reduces the activity of the pollutants by means of measures such as source control, agricultural regulation and control, soil improvement and phytoremediation, thereby reducing the risk of exceeding the standard of agricultural product pollutants and improving the environmental quality of the polluted cultivated land soil.
The existing method for regulating the pH value of soil, applying organic fertilizer and microorganism bacterial fertilizer is mainly adopted to reduce the migration capacity and bioavailability of heavy metals in soil through chelating, complexing, adsorbing, precipitating and other actions, so as to achieve the effect of reducing the total absorbable amount of the heavy metals, and has a certain effect on reducing the heavy metal residues of crops, but has limited effect; secondary pollution is introduced when the conventional soil conditioner and passivating agent are applied for a long time, the soil aggregate structure is damaged, the soil is hardened, the cultivated land force is reduced, the yield of the cultivated plow crops is affected, and the income of farmers is greatly affected.
The biotoxicity of heavy metals and the accumulation capacity of heavy metals in crops are not completely controlled by the total amount of heavy metals, but are determined by the bioavailability, root absorption and transfer of heavy metals in plants. The organic matters in the soil and other nutrient components, microorganisms and root systems form a special microecological system, the bioavailability of heavy metals in the soil is obviously influenced, the cell walls of the microorganisms mainly comprise mannose, glucan, protein and chitin, extracellular Polysaccharide (EPS) covered on the cell surfaces, polar functional groups on the cell walls and some chemical groups in the cells can be combined with metal ions, extracellular enrichment precipitation and cell surface adsorption or complexation are realized, a large number of microorganisms in the soil exist and the organic matters are increased, the heavy metal ions can be solidified, the bioavailability of the heavy metal ions is reduced, and the absorption of the root systems to the heavy metal ions is reduced.
At present, the schemes of conditioning the pH value of soil, applying organic fertilizer, applying microbial fertilizer and the like in the prior art have adverse effects on the structure and physicochemical properties of the soil after long-term application, are easy to introduce secondary pollution, and have no obvious effect of reducing heavy metals in plants. Aiming at the relation between plant root system absorption and soil microecology, the ecological chemistry combined restoration technology is used for heavy metal blocking, so that the heavy metal pollution of soil is solved under the condition of low-concentration spraying, and safe agricultural products can be produced in farmlands with medium and slight heavy metal pollution, which is a problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a blocking agent which can be used for blocking heavy metals by applying an ecological chemistry combined restoration technology, does not introduce secondary pollution and can obviously reduce the content of harmful heavy metals in plants under the condition of low-concentration spraying, and a use method and application thereof.
The invention solves the technical problems by adopting the following technical scheme:
the first object of the invention is to provide a barrier agent for reducing the content of harmful heavy metals in plants, which is characterized by comprising soluble phosphate, quaternized chitosan and N-acetylglucosamine.
Further, the blocking agent comprises the following raw materials in percentage by weight: 15-25% of soluble phosphate; quaternized chitosan, 20-30%; 10 to 15 percent of N-acetylglucosamine.
Further, the blocking agent is root Shi Zuge agent.
Further, the soluble phosphate is dihydrogen phosphate or diammonium phosphate.
Further, the monobasic phosphate is potassium monobasic phosphate or calcium monobasic phosphate.
The second object of the invention is to provide a method for using a barrier agent for reducing the content of harmful heavy metals in plants, which is characterized by comprising the following steps: the blocking agent is sprayed on the soil for the first time during the soil leveling and rotary tillage or the base fertilizer and the topdressing before the plant cultivation, and the blocking agent is sprayed on the soil at the root of the plant for the second time during the plant grouting period, the fruit expanding period or the color-changing sugar-increasing period.
Further, before use, preparing a blocking agent, mixing the soluble phosphate, the quaternized chitosan and the N-acetylglucosamine which are weighed according to a proportion, and then using water to fix the volume, so that the mass percentages of the raw materials in the prepared blocking agent are as follows: 15-25% of soluble phosphate; quaternized chitosan, 20-30%; 10 to 15 percent of N-acetylglucosamine.
Further, the barrier agent is diluted 50 times before the barrier agent is sprayed for the first time, and the barrier agent is diluted 100 times before the barrier agent is sprayed for the second time.
Further, for annual plants, the method for using the barrier comprises the following steps:
the blocking agent is sprayed for the first time on soil before plant cultivation in the soil leveling and rotary tillage, and then the blocking agent is sprayed for the second time on root soil in the plant grouting period or fruit expanding period and color-changing sugar-increasing period, so that the soil is kept to be sufficiently wetted in the spraying process.
Further, for perennial plants, the method of using the barrier agent comprises the steps of:
when base fertilizer or additional fertilizer is applied annually, the blocking agent is sprayed for the first time along the drip line of the tree crown by drip irrigation or mechanical pressure, and the blocking agent is sprayed for the second time in the fruit expanding period or one month before picking, so that the soil is kept sufficiently wet in the spraying process.
Furthermore, the barrier agent is sprayed at the root depth of 30-50 cm along the drip line of the crown by adopting a drip irrigation mode or mechanical pressure.
Further, the usage amount of the blocking agent is adjusted according to the content of heavy metals in the soil, and is 0.7 percent<P Heald When the total spraying amount is less than or equal to 1.0, the total spraying amount per mu is 0.5-1L; when 1.0<P Heald When the total spraying amount is less than or equal to 2.0, the total spraying amount is 1-2L per mu; when 2.0<P Heald When the total spraying amount is less than or equal to 3.0, the total spraying amount is 2-3L per mu; p (P) Heald Is the comprehensive pollution index of the heavy metals in the soil.
Further, the calculation formula of the single pollution index of the heavy metal i for evaluating the pollution degree of the heavy metal in the soil is as follows:
Pi＝Ci/Si
wherein Pi is a single pollution index of heavy metal i in the soil at a sampling point, ci is an actual measurement value of the content of heavy metal i, and Si is a pollution content initial critical value of the heavy metal i. Pi is less than or equal to 1, which indicates that the pollution is not caused, and comprehensive pollution index evaluation is not performed any more; pi >1 indicates contaminated, and is further evaluated using the integrated contamination index.
The calculation formula of the inner Mei Luo comprehensive pollution index for evaluating the soil heavy metal pollution degree is as follows:
P heald ＝{(P 2 imax +P 2 iave )/2} 1/2
P in the formula Heald Is the comprehensive pollution index of the soil heavy metal at the sampling point, P 2 imax Is the maximum value of the single pollution index of heavy metals in soil, P 2 iave Is the average value of the single pollution indexes of heavy metals in soil. P (P) Heald 5 classes of the grading standard of (C), respectively P Heald Less than or equal to 0.7 and is clean, 0.7<P Heald Less than or equal to 1.0 is still clean (guard limit), 1.0<P Heald Less than or equal to 2.0 is slight pollution, 2.0<P Heald Less than or equal to 3.0 is moderate pollution, P Heald >3.0 is heavy contamination.
Further, the blocking agent is used alone as root Shi Zuge agent.
Further, the barrier agent is used as a fertilizer additive in combination with a fertilizer.
Further, the fertilizer comprises an organic fertilizer and a biological fertilizer.
Further, the blocking agent is a lead, cadmium and chromium heavy metal blocking agent.
The third object of the invention is to provide an application of the blocking agent in reducing the content of heavy metals such as lead, cadmium and chromium in plants.
The invention reduces the content of harmful heavy metals in plants, especially the content of lead, cadmium and chromium heavy metals in plants by an ecological chemistry combined restoration technology.
The soluble phosphate is added to react with heavy metal ions in the soil, root systems and stems in a chemical precipitation manner, so that the in-situ passivation and blocking of the heavy metals are realized, the absorption of the root systems and the migration from the root systems to edible parts are reduced, and the redundant phosphate can be absorbed by plants as phosphate fertilizer, so that no residue exists and no secondary pollution is caused.
The N-acetylglucosamine is increased, the rapid mass propagation of microorganisms in the soil is promoted, the microecology of the soil is activated, the bioavailability of heavy metal ions is reduced by biological adsorption and solidification, and the migration of the heavy metal from the soil to root hair cells is reduced.
The amino and hydroxyl in the molecule of the quaternized chitosan can be subjected to chelation reaction with metal ions to adsorb heavy metal ions, so that migration of heavy metal from soil to root hair cells is reduced, meanwhile, soil aggregates can be rapidly formed in the soil as macromolecular organic matters, soil is loosened, physical properties of the soil are improved, good soil microenvironment is provided for beneficial microorganisms, the amino and hydroxyl can be slowly degraded into N-acetamido glucose, and the soil microecology is continuously activated for a long time.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the invention can obviously reduce the content of harmful heavy metals in plants under the condition of low-concentration spraying, is greatly lower than the limit requirement in national standard foods, and has obvious barrier effect on the harmful heavy metals.
2. The ecological influence is small. The invention integrates the technologies of microecological restoration, plant passivation and chemical restoration, focuses on coordination with natural ecological processes, does not form secondary pollution and does not influence the safety of agricultural products.
3. The cost is low. The invention draws advantages of micro-ecological restoration, and the cost is lower than that of micro-ecological restoration.
4. The blocking agent can be prepared into aqueous solution for independent spraying, can also be used as an additive of other fertilizers such as organic fertilizers, biological fertilizers and the like, enhances the blocking effect on harmful heavy metals, and is convenient to popularize.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
In addition, unless otherwise specifically indicated, the various raw materials, reagents, instruments and equipment used in the present invention may be obtained commercially or prepared by existing methods.
Example 1 Rice field verification test
The test base is an exemplary project of heavy metal solidification passivation test points of a heavy-cadmium polluted farmland. Through on-site investigation and soil environment quality evaluation, and rice planting field management, a barrier technology implementation plan is formed, and project implementation scheme is formed.
The 400 mu rice test-spot farmland is divided into 8 areas, each area is 50 mu, 2 m protection rows are set in each area, and 4 experimental groups and 4 control groups are arranged randomly. Sampling, preserving, processing and analyzing and testing soil samples are carried out according to the technical Specification for soil environmental monitoring (HT/J166-2004), after accumulated water at the upper part of a paddy field is drained before sampling, 10 sampling points are arranged in a test base according to a chessboard type, 0-20 cm surface soil is equivalently collected, uniformly mixed, sundries are removed, naturally air-dried, crushed, screened by a nylon screen, leached by aqua regia, the content of lead, cadmium and chromium is measured by adopting an atomic absorption spectrophotometry, and the soil comprehensive pollution index is calculated.
The calculation formula of the single pollution index of the heavy metal i for evaluating the pollution degree of the heavy metal in the soil is as follows:
Pi＝Ci/Si
wherein Pi is a single pollution index of heavy metal i in the soil at a sampling point, ci is an actual measurement value of the content of heavy metal i, and Si is a pollution content initial critical value of the heavy metal i. Pi is less than or equal to 1, which indicates that the pollution is not caused, and comprehensive pollution index evaluation is not performed any more; pi >1 indicates contaminated, and is further evaluated using the integrated contamination index.
The calculation formula of the inner Mei Luo comprehensive pollution index for evaluating the soil heavy metal pollution degree is as follows:
P heald ＝{(P 2 imax +P 2 iave )/2} 1/2
P in the formula Heald Is the comprehensive pollution index of the soil heavy metal at the sampling point, P 2 imax Is the maximum value of the single pollution index of heavy metals in soil, P 2 iave Is the average value of the single pollution indexes of heavy metals in soil. P (P) Heald 5 classes of the grading standard of (C), respectively P Heald Less than or equal to 0.7 and is clean, 0.7<P Heald Less than or equal to 1.0 is still clean (guard limit), 1.0<P Heald Less than or equal to 2.0 is slight pollution, 2.0<P Heald Less than or equal to 3.0 is moderate pollution, P Heald >3.0 is heavy contamination. When 0.7<P Heald When the total spraying amount is less than or equal to 1.0, the total spraying amount per mu is 0.5-1L; when 1.0<P Heald When the total spraying amount is less than or equal to 2.0, the total spraying amount is 1-2L per mu; when 2.0<P Heald When the total spraying amount is less than or equal to 3.0, the total spraying amount is 2-3L per mu.
Determining the soil comprehensive pollution index P according to calculation Heald 0.9, thereby determining the spraying amount of the blocking agent per mu to be 0.5L. Spraying the blocking agent of the invention to the experimental group, applying irrigation water to the control group, wherein the fertilization, the planting time, the pesticide and the daily field management of each area are the same, and harvesting is unified after maturation. The composition of the barrier agent in this example is shown in table 1:
TABLE 1 composition of Rice Barrier
In this embodiment, the preparation method of the rice barrier agent comprises the following steps: weighing 150g of monopotassium phosphate, 200g of quaternized chitosan and 150g of N-acetylglucosamine, mixing, dissolving with water, and fixing the volume to 1L in a volumetric flask for standby.
The blocking agent is sprayed for the first time, and the blocking agent is synchronously sprayed when the paddy field is ploughed in the early 4 months. Measuring 0.5L of blocking agent, diluting by 50 times, loading into a spraying device, fixing the spraying device on a rotary cultivator, and synchronously spraying soil during rotary cultivation to ensure that the blocking agent is uniformly combined with the soil on the rotary cultivation surface, and keeping uniform spraying amount in the implementation process.
And spraying the blocking agent for the second time, wherein 0.5L of the blocking agent is measured in the rice grouting period, and after 100 times of dilution, the blocking agent is sprayed to the soil in an unmanned aerial vehicle mode, and the spraying amount is kept uniform in the spraying process.
The test base rice growth period is about 160 days, the root of the test base rice is turned over in middle and late 3 months, the test base rice is transplanted after 4 months of initial ploughing and watering, and 5 months of watering is performed; and (5) field sunning in the late 7 months and unified harvesting at the bottom of 8 months. And the rice to be inspected is subjected to joint sample selection and collection by farmers, village committee and planting enterprises, and is sent to Shanghai general standard SGS to detect the content of heavy metal cadmium. The detection pair of the average content of the heavy metals of lead, cadmium and chromium in the experimental group and the average content of the heavy metals of the control group are shown in table 2:
table 2 comparative table for detecting heavy metal contents in rice experimental group and control group
( And (3) injection: ND is that the heavy metal content is below the detection quantitative limit and cannot be detected; 2. the limit standard of the cadmium content in national standard food is 0.1mg/kg )
As can be seen from the table, the cadmium content of the rice experimental group is reduced by 75.1% compared with the control group, and the content of heavy metals such as lead, cadmium and chromium in the rice is obviously reduced compared with that of the barrier agent sprayed by the method, and the effect of reducing the heavy metal content in plants is obvious.
Example 2 Pepper field verification test
And carrying out harmful heavy metal blocking verification tests on Chongqing pepper planting bases, carrying out on-site investigation, evaluating the quality of soil environment, combining with pepper planting field management, forming a blocking technology implementation plan, and programming project implementation scheme.
The 600 mu pepper experiment base is divided into 6 areas, each area is 100 mu, 2 m protection rows are set in each area, and 3 experiment groups and 3 control groups are arranged randomly. Sampling of soil samples of this example was the same as in example 1, rootCalculating and determining soil comprehensive pollution index P Heald 1.2, thereby determining a spray level of 1.5L per mu of barrier agent. The blocking agent is sprayed to the experimental group, irrigation water is applied to the control group, fertilization and planting time of each area, pesticide and daily field management are the same, and the blocking agent is harvested uniformly after maturation. The composition of the barrier agent in this example is shown in table 3:
TABLE 3 composition of Zanthoxylum bungeanum blocking agent
The method of preparing the pricklyash peel blocking agent in this embodiment is described in example 1.
The blocking agent is sprayed for the first time, and the blocking agent is synchronously implemented when the Chinese prickly ash is ditched and applied with the organic base fertilizer. 1.5L of blocking agent is measured per mu of land, diluted by 50 times, sprayed on the base fertilizer and ditching soil, the blocking agent is uniformly combined with root system soil, and soil is covered after spraying.
And spraying the blocking agent for the second time, wherein the swelling period is selected after the initial bud of the pricklyash peel is at the end of four months, 1.5L of the blocking agent is measured per mu of land, and the spraying of root system soil is completed in a drip irrigation mode after 100 times dilution.
And (5) performing screening and harvesting on the pepper by combining the agricultural park and the planting enterprise, and performing detection on the pepper by sending Shanghai through mark SGS. The detection pair of the average content of the heavy metals cadmium, lead and chromium in the experimental group and the average content of the heavy metals in the control group are shown in table 4:
table 4 comparison table for heavy metal content detection of pricklyash peel experimental group and control group
( And (3) injection: ND is that the heavy metal content is below the detection quantitative limit and cannot be detected; 2. the limit standard of the cadmium content in national standard food is 0.11mg/kg )
As can be seen from the table, the lead content of the pricklyash peel experimental group is reduced by 85.9% compared with the control group, the cadmium content is reduced by 68.6% compared with the control group, the national standard requirement of the pricklyash peel is met, the chromium content can not be detected (the detection quantitative limit is 0.1 mg/kg), and the effects of obviously reducing the heavy metal content in plants are obvious because the heavy metal lead and cadmium content in the pricklyash peel is less than the heavy metal content in the pricklyash peel after the barrier agent is sprayed according to the method of the invention.
Example 3 tea field verification test
And carrying out harmful heavy metal blocking verification tests on the Guangxi tea planting bases, and forming a blocking technology implementation plan and programming project implementation plan by on-site investigation, soil environment quality evaluation and planting field management.
The tea experiment base is divided into 4 areas with the area of 100 mu, each area is 25 mu, 2 m protection rows are set in each area, and 2 experiment groups and 2 control groups are arranged randomly. Soil was sampled, treated, analyzed and tested as in example 1 to determine the soil integrated pollution index P Heald 2.1, thereby determining a spray level of 2.5L per mu of barrier agent. And spraying a blocking agent to the experimental group, and not spraying the blocking agent to the control group, wherein the fertilization, the planting time, the pesticide and the daily field management of each area are the same, and the harvesting is unified after the maturation. The composition of the barrier agent in this example is shown in table 5:
TABLE 5 composition of tea Barrier
In this example, the method of preparing the tea barrier is described in example 1.
Spraying the blocking agent for the first time, selecting 11 months after the base fertilizer is applied, measuring 2.5L of the blocking agent, diluting 50 times, selecting 2-3 points on average for each tea tree, spraying soil at a position 30-50 cm away from the root of the tea tree by using a pressure gun, and keeping the soil sufficiently wet in the spraying process at a depth of about 20-30cm, wherein the surface of the earth is free from water accumulation.
Spraying the blocking agent for the second time, selecting the first month of picking the spring tea for 3 months, measuring 2.5L of the blocking agent, diluting by 100 times, and spraying the soil, wherein the spraying process is consistent with the first spraying.
After the tea leaves are picked by the tea leaf center, the tea leaves are sent to Shanghai general standard SGS to detect the content of heavy metals such as lead, cadmium and chromium. The test pair of the average heavy metal content of the experimental group and the average heavy metal content of the control group are shown in table 6:
table 6 comparison table for heavy metal content detection of tea experimental group and control group
( And (3) injection: ND indicates that the heavy metal content is below the detection quantitative limit and cannot be detected )
As can be seen from the table, the cadmium content of the tea experimental group is reduced by 81.6% compared with the control group, and the chromium content is reduced by 93.1% compared with the control group. After the blocking agent is sprayed by the method, the content of heavy metal chromium and cadmium in the tea is obviously reduced compared with the spraying blocking agent, and the effect of reducing the content of heavy metal in plants is obvious.
The foregoing embodiment numbers of the present invention are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
While the present invention has been described with reference to the above-described embodiments, it is to be understood that the same is not limited to the above-described embodiments, but rather that the same is intended to be illustrative only, and that many modifications may be made by one of ordinary skill in the art without departing from the spirit of the invention and scope of the appended claims.
Claims (5)
1. The application method of the barrier agent for reducing the content of harmful heavy metals in plants is characterized by comprising the following steps of: before use, preparing a blocking agent, mixing the soluble phosphate, the quaternized chitosan and the N-acetylglucosamine which are weighed according to a proportion, and then using water to fix the volume, so that the mass percentages of the raw materials in the prepared blocking agent are as follows: 15-25% of soluble phosphate; quaternized chitosan, 20-30%; 10-15% of N-acetylglucosamine; the soluble phosphate is dihydrogen phosphate or diammonium phosphate;
firstly spraying a blocking agent to soil before plant cultivation in the soil leveling, rotary tillage or base fertilizer application and topdressing, and secondly spraying the blocking agent to plant root soil in the plant grouting period, fruit swelling period or color-changing sugar-increasing period; the blocking agent is a heavy metal blocking agent of lead, cadmium and chromium.
2. The method of using a barrier agent for reducing the content of harmful heavy metals in plants according to claim 1, wherein: the barrier agent is diluted by 50 times before the barrier agent is sprayed for the first time, and the barrier agent is diluted by 100 times before the barrier agent is sprayed for the second time.
3. The method of using a barrier agent for reducing the content of harmful heavy metals in plants according to claim 1 or 2, wherein the amount of the barrier agent is adjusted according to the content of heavy metals in soil to 0.7<P Heald When the total spraying amount is less than or equal to 1.0, the total spraying amount per mu is 0.5-1L; when 1.0<P Heald When the total spraying amount is less than or equal to 2.0, the total spraying amount is 1-2L per mu; when 2.0<P Heald When the total spraying amount is less than or equal to 3.0, the total spraying amount is 2-3L per mu; p (P) Heald Is the comprehensive pollution index of the heavy metals in the soil.
4. A method of using a barrier agent for reducing the content of harmful heavy metals in plants according to claim 3, wherein said barrier agent is used alone as root Shi Zuge agent.
5. A method of using a barrier agent for reducing the content of harmful heavy metals in plants as set forth in claim 3, wherein: the blocking agent is used as a fertilizer additive and is combined with a fertilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211041772.0A CN115340875B (en) | 2022-08-29 | 2022-08-29 | Barrier agent for reducing content of harmful heavy metals in plants, use method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211041772.0A CN115340875B (en) | 2022-08-29 | 2022-08-29 | Barrier agent for reducing content of harmful heavy metals in plants, use method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115340875A CN115340875A (en) | 2022-11-15 |
| CN115340875B true CN115340875B (en) | 2023-06-13 |
Family
ID=83954090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211041772.0A Active CN115340875B (en) | 2022-08-29 | 2022-08-29 | Barrier agent for reducing content of harmful heavy metals in plants, use method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340875B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321484A (en) * | 2011-06-09 | 2012-01-18 | 山东省农业科学院农业资源与环境研究所 | Organic environmentally-friendly soil conditioner for improving acidified or acid soil |
| CN111073658A (en) * | 2019-11-21 | 2020-04-28 | 河北建设集团安装工程有限公司 | Heavy metal contaminated soil remediation agent and preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1337166A (en) * | 2000-08-16 | 2002-02-27 | 山东解奥生物技术有限公司 | Crop expellant for preventing heavy metal and pesticide pollution and its prepn |
| JP4443290B2 (en) * | 2004-04-15 | 2010-03-31 | 株式会社テルナイト | Purification method for heavy metal contaminated soil |
| CN104560047B (en) * | 2014-12-03 | 2017-12-22 | 成都新朝阳作物科学有限公司 | Soil heavy metal passivant and application thereof |
| CN108046902A (en) * | 2017-12-12 | 2018-05-18 | 北京本农科技发展有限公司 | Blade face resistance control agent, preparation method and the method for reducing crops cadmium pollution |
| CN108675883A (en) * | 2018-08-07 | 2018-10-19 | 湖南艾布鲁环保科技股份有限公司 | Soil activating agent, preparation method and its application for cadmium pollution soil repair |
| CN109485504A (en) * | 2018-12-18 | 2019-03-19 | 佛山市铁人环保科技有限公司 | A kind of foliar fertilizer and preparation method thereof obstructing Metal uptake |
| CN110918638A (en) * | 2020-01-17 | 2020-03-27 | 湖南超富集生态科技有限公司 | Method for activating and repairing arsenic-polluted soil by using ciliate desert-grass |
| CN111995465B (en) * | 2020-09-04 | 2022-07-19 | 上海贯发海洋生物科技有限公司 | Heavy metal blocking agent, application and use method thereof |
| CN114918243B (en) * | 2022-05-13 | 2024-05-24 | 沈阳瑞丰农业技术开发有限公司 | Repairing agent and repairing method for repairing heavy metal pollution of soil |
-
2022
- 2022-08-29 CN CN202211041772.0A patent/CN115340875B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321484A (en) * | 2011-06-09 | 2012-01-18 | 山东省农业科学院农业资源与环境研究所 | Organic environmentally-friendly soil conditioner for improving acidified or acid soil |
| CN111073658A (en) * | 2019-11-21 | 2020-04-28 | 河北建设集团安装工程有限公司 | Heavy metal contaminated soil remediation agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115340875A (en) | 2022-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107695088B (en) | Method for restoring As-Cd combined polluted farmland soil by utilizing hyper-enriched plant biomass charcoal combined system | |
| Settineri et al. | Effects of different thinning intensities on soil carbon storage in Pinus laricio forest of Apennine South Italy | |
| Schomberg et al. | Nutrient dynamics of crop residues decomposing on a fallow no‐till soil surface | |
| Li et al. | Crop cultivation and intensive grazing affect organic C pools and aggregate stability in arid grassland soil | |
| CN111080097A (en) | Comprehensive assessment method for agricultural non-point source and heavy metal pollution risk | |
| Maier et al. | Effect of current-season application of calcitic lime on soil pH, yield and cadmium concentration in potato (Solanum tuberosum L.) tubers | |
| Wang et al. | Variations in cadmium accumulation and distribution among different oilseed rape cultivars in Chengdu Plain in China | |
| CN107286943A (en) | A kind of cadmium passivator and its production method with improved soil function | |
| Oijagbe et al. | Effects of heavy metals on soil microbial biomass carbon | |
| Ibarra-Flores et al. | Soil physicochemical changes following buffelgrass establishment in Mexico | |
| Wang et al. | Several newly discovered Mo-enriched plants with a focus on Macleaya cordata | |
| CN115340875B (en) | Barrier agent for reducing content of harmful heavy metals in plants, use method and application | |
| Sarkar et al. | Plant availability of boron in acid soils as assessed by different extractants | |
| Yang et al. | Chemical fractions and phytoavailability of copper to rape grown in the polluted paddy soil | |
| CN112645766A (en) | Organic water-soluble fertilizer for repairing cadmium-polluted farmland | |
| Li et al. | Soil Boron Content and the Effects of Boron Application on Yields of Maize, Soybean, Rice and Sugarbeet in Heilongjiang Province, PR China | |
| CN108405587B (en) | Method for restoring cash crops in heavy metal contaminated soil | |
| Jiang et al. | Exploring the effects of one-time biochar application with low dosage on soil health in temperate climates | |
| CN111234825A (en) | Biochar for improving saline-alkali soil, preparation method, preparation and application of derivatives thereof | |
| Messier et al. | Growth of western red cedar seedlings in relation to microtopography, forest floor nutrient status, and fireweed and salal on clear-cut sites in coastal British Columbia | |
| Wynne et al. | Canola emergence and early growth were not affected by allelopathic properties of wheat residue | |
| Vetturayasudharsanan et al. | Assessment of soil properties from coir pith waste dump yard | |
| Debnath et al. | Critical limit of available boron for rice in alluvial zone soils of West Bengal | |
| CN106688546B (en) | A method for improving the sensitivity and specificity of bryophytes to detect soil cadmium pollution | |
| CN109593530A (en) | It is a kind of to adsorb multiple heavy metal cation passivator and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |