CN115231709B - Application of iron film in improving restoration of heavy metal chromium-polluted water body by super-enriched plant Leersia hexandra - Google Patents
Application of iron film in improving restoration of heavy metal chromium-polluted water body by super-enriched plant Leersia hexandra Download PDFInfo
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- CN115231709B CN115231709B CN202210855612.3A CN202210855612A CN115231709B CN 115231709 B CN115231709 B CN 115231709B CN 202210855612 A CN202210855612 A CN 202210855612A CN 115231709 B CN115231709 B CN 115231709B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 240000003483 Leersia hexandra Species 0.000 title claims abstract description 73
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 57
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 45
- 241000196324 Embryophyta Species 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 31
- 230000006698 induction Effects 0.000 claims description 24
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 11
- 238000012258 culturing Methods 0.000 claims description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 229910052564 epsomite Inorganic materials 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 239000011686 zinc sulphate Substances 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- 229910004878 Na2S2O4 Inorganic materials 0.000 claims description 4
- 229910018890 NaMoO4 Inorganic materials 0.000 claims description 4
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 abstract description 14
- 230000029553 photosynthesis Effects 0.000 abstract description 5
- 238000010672 photosynthesis Methods 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 244000025254 Cannabis sativa Species 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229930002875 chlorophyll Natural products 0.000 description 8
- 235000019804 chlorophyll Nutrition 0.000 description 8
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 239000007836 KH2PO4 Substances 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052603 melanterite Inorganic materials 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001521474 Liriope <hydrozoan> Species 0.000 description 1
- 241001081179 Litsea Species 0.000 description 1
- 235000012854 Litsea cubeba Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 108010074506 Transfer Factor Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 210000003763 chloroplast Anatomy 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to the technical field of water environment heavy metal pollution treatment, and particularly relates to application of an iron film in improving the restoration of heavy metal polluted water bodies by super-enriched plant Leersia hexandra. The iron film can reduce the damage of heavy metal chromium to the photosynthesis of Leersia hexandra, obviously improve the heavy metal content and the transport factor of the overground part of Leersia hexandra, and improve the capability of the Leersia hexandra in restoring chromium-polluted water bodies.
Description
Technical Field
The invention belongs to the technical field of water environment heavy metal pollution treatment, and particularly relates to application of an iron film in improving chromium super-enriched plant Leersia hexandra and repairing heavy metal chromium-polluted water bodies.
Background
Chromium (Cr) is widely used in the industrial manufacturing industries of electroplating, tanning, printing and dyeing, but is itself a very hazardous environmental pollutant. Chromium is generally present in aqueous environments in the form of trivalent chromium (Cr (III)) and hexavalent chromium (Cr (VI)), where Cr (VI) has a strong environmental mobility and high bioavailability, with a toxicity threat of 100 times that of Cr (III), a more "three-way" high risk substance for humans. Therefore, chromium pollution in water is one of the environmental problems to be solved urgently.
The Leersia hexandra is a wet chromium super-enriched plant reported for the first time in China, has excellent capability of absorbing and enriching chromium from silt or water body, and has the advantages of high growth speed and short harvesting period. Compared with the traditional materialized restoration method with high cost and easy secondary pollution, the restoration method for restoring the chromium-polluted water body by utilizing the chromium super-enrichment performance of the Leersia hexandra, is a green, low-cost and extremely-application-prospect heavy metal pollution restoration technology.
The efficiency of the super-enriched plants in removing heavy metals depends on the biomass size of the plants themselves, the content of the heavy metals enriched and the size of the transport factor of the heavy metals from the underground part to the above-ground part. In order to increase plant extraction, the prior art generally employs chemical assisted phytoremediation techniques, using synthetic or organic chelating agents, to increase the bioavailability of metals such as ethylenediamine tetraacetic acid (EDTA) and diethylenetriamine pentaacetic acid (DTPA), among others. However, these chelating agents also have significant drawbacks in the application process, such as EDTA itself tends to be toxic and not readily biodegradable, and the high price also limits its use on a large scale.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides application of an iron film in improving chromium super-enriched plant Leersia hexandra and repairing heavy metal chromium-polluted water, improving the chromium content of overground parts of Leersia hexandra and improving the capability of Leersia hexandra in repairing chromium-polluted water.
The invention also provides a method for improving the restoration of the water body polluted by the heavy metal chromium by the Leersia hexandra, which comprises the following steps: mixing the plant culture solution without Fe and KH 2PO4 with exogenous ferrous ions, and inducing and culturing the root surface of Leersia hexandra to generate an iron film.
Preferably, the concentration of the exogenous ferrous ions is 25-100 mg/L; the time of the induction culture is 2-3 d; the initial pH value of the induction culture is 5.9-6.1.
Preferably, the induction culture comprises light culture and dark culture, wherein the temperature of the light culture is 30 ℃, the temperature of the dark culture is 20 ℃, and the illumination time is 12-14 h/d.
Preferably, before the induction culture, the method further comprises: cleaning the Leersia hexandra root surface by adopting a DCB solution.
Preferably, the DCB solution includes 0.003mol/L Na3C6H5O7·2H2O,0.0125mol/LNaHCO3、0.020mol/LNa2S2O4 and the balance water.
Preferably, before the induction culture, the method further comprises: culturing the pretreated Leersia hexandra by using a plant culture solution which does not contain Fe and KH 2PO4 for 12-24 h.
Preferably, after the induction culture is finished, the method further comprises: culturing Lestus by using a plant culture solution without Fe for 12-24 hours.
Preferably, the plant culture solution comprises 5mmol/L Ca(NO3)2·4H2O、1mmol/LKH2PO4、5mmol/L KNO3、2mmol/L MgSO4·7H2O、0.02mmol/L FeSO4·7H2O、0.3μmol/LCuSO4·5H2O、0.045mmol/L H3BO3、0.01mmol/L MnCl2·4H2O、0.8μmol/LZnSO4·7H2O、0.1μmol/LNaMoO4·2H2O、0.02mmol/LNa2-EDTA and the balance water.
Preferably, the pH value of the plant culture solution is 5.9-6.1.
The invention provides an application of an iron film in improving the restoration of heavy metal chromium polluted water bodies by super-enriched plant Leersia hexandra. The iron film can reduce the damage of heavy metal chromium to the photosynthesis of Leersia hexandra, obviously improve the heavy metal content and the transport factor of the overground part of Leersia hexandra, and improve the capability of the Leersia hexandra in restoring chromium-polluted water bodies.
The invention utilizes ferrous ions to oxidize on the root surface of plants to generate a large amount of weak crystalline ferrihydrite and a small amount of goethite, wurtzite and other crystalline ferrite (hydroxide) which are coated on the root surface in a film state to form a reddish brown iron film, and utilizes the special physicochemical properties of the iron film on the root surface to improve the capability of the Lei standing grain for repairing chromium-polluted water.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments will be briefly described below.
FIG. 1 is an SEM image of the root table of Leersia hexandra before washing with DCB solution in example 1;
FIG. 2 is an SEM image of the root table of Leersia hexandra after cleaning with DCB solution in example 1;
FIG. 3 is a graph showing the measurement results of Fe content in iron films obtained by different treatment methods;
FIG. 4 is a graph showing the measurement results of total chlorophyll content in the leaves of Leersia hexandra under different treatment modes;
FIG. 5 shows the chromium content of the Leersia hexandra root surface iron film in various treatments.
Detailed Description
The invention provides an application of an iron film in improving the restoration of heavy metal chromium polluted water bodies by super-enriched plant Leersia hexandra.
The iron film disclosed by the invention can be used for reducing the damage of heavy metal chromium to the photosynthesis of Leersia hexandra, remarkably improving the content of heavy metal chromium in the overground part of Leersia hexandra and the transfer factor, and improving the capability of the Leersia hexandra in repairing chromium-polluted water bodies.
The invention also provides a method for improving the restoration of the water body polluted by the heavy metal chromium by the super-enriched plant Leersia hexandra, which comprises the following steps: mixing plant culture solution without Fe and KH 2PO4 with exogenous ferrous ion, and inducing to culture Lei grass.
Before the Leersia hexandra is induced and cultured, the Leersia hexandra is preferably pretreated to obtain pretreated Leersia hexandra. The pretreatment according to the present invention preferably includes a first pretreatment and a second pretreatment. The first pretreatment preferably cleans the table of Leersia hexandra roots with a DCB solution; the DCB solution preferably includes 0.003mol/LNa3C6H5O7·2H2O,0.0125mol/LNaHCO3、0.020mol/LNa2S2O4 and the balance water. The pretreatment time of the invention is preferably 30 to 60 minutes, more preferably 40 to 50 minutes, and even more preferably 45 minutes; the solvent of the DCB solution is preferably water, and more preferably deionized water. The purity of each component in the DCB solution is analytically pure. The DCB solution can remove iron films formed in the natural growth process of the Leersia hexandra, and does not damage plants.
The second pretreatment according to the present invention preferably comprises culturing the first pretreated Lei's grass with a plant broth free of Fe and KH 2PO4. The time of the culture according to the present invention is preferably 12 to 24 hours, more preferably 24 hours. The plant culture solution which does not contain Fe and KH 2PO4 preferably comprises 5mmol/L Ca(NO3)2·4H2O、5mmol/L KNO3、2mmol/L MgSO4·7H2O、0.3μmol/L CuSO4·5H2O、0.045mmol/L H3BO3、0.01mmol/L MnCl2·4H2O、0.8μmol/L ZnSO4·7H2O、0.1μmol/LNaMoO4·2H2O and 0.02mmol/LNa 2 -EDTA; the pH value of the plant culture solution is preferably 5.9-6.1, and more preferably 6.0; the solvent of the plant culture solution is preferably water, and more preferably deionized water. The pH regulator of the plant culture solution is preferably NaOH of 0.1 mol/L. The purity of each component in the plant culture solution which does not contain Fe and KH 2PO4 is analytically pure. The second pretreatment provided by the invention has a dephosphorization effect, and can prevent phosphorus from reacting with Fe compounds to generate precipitate substances in the subsequent induction culture, and the Leersia hexandra after the second pretreatment provided by the invention can generate an iron film on the root surface more easily.
The plant culture solution without Fe and KH 2PO4 is mixed with exogenous ferrous ions (Fe (II)) to induce and culture the pretreated Lei grass. The concentration of the exogenous ferrous ions is preferably 25-200 mg/L, and more preferably 50mg/L. In the specific implementation process, the method can take any value within the range of 25-200 mg/L, and specifically, the concentration of the exogenous ferrous ions can be 25mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L or 100mg/L. The exogenous ferrous ion is preferably FeSO 4·7H2 O. The composition of the plant culture solution without Fe and KH 2PO4 according to the present invention is preferably consistent with the foregoing, and will not be described in detail herein.
In the present invention, the induction culture preferably includes light culture and dark culture, and the time of the light culture is preferably 12 to 14h/d, more preferably 14h/d; the temperature of the light culture is preferably 30 ℃; the temperature of the dark culture is preferably 20 ℃. In the induction culture process, the invention preferably uses tin foil or aluminum foil to shade the culture container in the whole process.
In the present invention, the time of the induction culture is preferably 2 to 3 days, more preferably 3 days; the initial pH of the induction culture is preferably 5.9 to 6.1, more preferably 6.0.
After the induction culture is finished, the invention preferably utilizes a plant culture solution which does not contain Fe to culture the Leersia hexandra after the induction culture; the time of the culture is preferably 12 to 24 hours, more preferably 24 hours. In the practice of the invention, the Fe-free plant broth preferably comprises 5mmol/L Ca(NO3)2·4H2O、5mmol/L KNO3、2mmol/L MgSO4·7H2O、1mmol/L KH2PO4、0.3μmol/L CuSO4·5H2O、0.045mmol/LH3BO3、0.01mmol/L MnCl2·4H2O、0.8μmol/L ZnSO4·7H2O、0.1μmol/LNaMoO4·2H2O and 0.02mmol/LNa 2 -EDTA. The solvent of the Fe-free plant culture solution according to the present invention is preferably water, and more preferably deionized water. The pH regulator of the plant culture solution without Fe is preferably NaOH of 0.1 mol/L; the purity of each component in the plant culture solution without any valence state Fe is analytically pure. According to the invention, the plant culture solution without any valence state Fe is used for culturing the induced and cultured Leersia hexandra, so that the unstable Fe phase on the root surface can be removed.
According to the invention, an exogenous ferrous ion is added into the plant culture solution, so that a layer of reddish brown iron film can be formed on the root surface of the Leersia hexandra before chromium stress, the existence form of chromium ions in the rhizosphere environment of the Leersia hexandra is changed through the special property of the root surface iron film after the chromium stress, the bioavailability of the chromium ions is improved, the transfer capability of the root of the Leersia hexandra in the Leersia hexandra tissue to the overground part is improved, and the capability of the Leersia hexandra for repairing heavy metal chromium-polluted water bodies is improved. The results of the examples show that after 50mg/L Fe (II) induces the formation of the root surface iron film, the chromium content of the overground part of the Lei's Po can be improved by about 20% compared with that of Lei's Po which naturally grows the iron film under the stress of 10mg/L Cr (VI) for 9d, and the transfer coefficient of the root to the overground part is increased from 0.23 to 0.30. The invention can improve the capability of the Leersia hexandra in repairing the chromium-polluted water body by utilizing the special physical and chemical properties of the root surface iron film, and improve the effect of the Leersia hexandra in repairing the heavy metal chromium-polluted water body.
The technical solutions provided by the present invention are described in detail below with reference to the drawings and examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
1. Reagent preparation
(1) Plant culture solutions and DCB solutions were prepared according to the formulations of tables 1 and 2, wherein the pH was adjusted to 5.9-6.1 with 0.1mol/L NaOH after the plant culture solution was prepared.
Table 1 plant broth formulation
| Compounds of formula (I) | Concentration of |
| Ca(NO3)2·4H2O | 5mmol/L |
| KNO3 | 5mmol/L |
| MgSO4·7H2O | 2mmol/L |
| KH2PO4 | 1mmol/L |
| FeSO4·7H2O | 0.02mmol/L |
| CuSO4·5H2O | 0.3μmol/L |
| H3BO3 | 0.045mmol/L |
| MnCl2·4H2O | 0.01mmol/L |
| ZnSO4·7H2O | 0.8μmol/L |
| NaMoO4·2H2O | 0.1μmol/L |
| Na2-EDTA | 0.02mmol/L |
| Deionized water | Allowance of |
TABLE 2DCB solution formulation
| Compounds of formula (I) | Concentration of |
| Na3C6H5O7·2H2O | 0.003mol/L |
| NaHCO3 | 0.0125mol/L |
| Na2S2O4 | 0.020mol/L |
| Deionized water | Allowance of |
(2) Preparing a plant culture solution without Fe and KH 2PO4 according to the formula of Table 3, wherein the pH of the plant culture solution without Fe and KH 2PO4 is regulated to 5.9-6.1 by 0.1mol/L NaOH after preparing the plant culture solution;
table 3 plant broth formulation free of Fe and KH 2PO4
(3) Preparing a plant culture solution without any valence state Fe according to the formula of the table 4, wherein the pH value of the plant culture solution without any valence state Fe is regulated to 5.9-6.1 by 0.1mol/L NaOH after the plant culture solution without any valence state Fe is prepared;
Table 4 formula of Fe-free plant culture solution
| Compounds of formula (I) | Concentration of |
| Ca(NO3)2·4H2O | 5mmol/L |
| KNO3 | 5mmol/L |
| MgSO4·7H2O | 2mmol/L |
| KH2PO4 | 1mmol/L |
| CuSO4·5H2O | 0.3μmol/L |
| H3BO3 | 0.045mmol/L |
| MnCl2·4H2O | 0.01mmol/L |
| ZnSO4·7H2O | 0.8μmol/L |
| NaMoO4·2H2O | 0.1μmol/L |
| Na2-EDTA | 0.02mmol/L |
| Deionized water | Allowance of |
2. The Lishi standing grain with good growth, complete root system and plant height of about 60cm is selected, thoroughly washed by deionized water, transferred into triangular bottles with the capacity of 1L by taking 30-40 plants as a group, and wrapped and shielded by tin foil or aluminum foil paper. The roots of the Lei Pos are soaked in the DCB solution obtained in the step 1 for 30-60 minutes, SEM images of the surfaces of the Lei Pos before the DCB solution is soaked are shown in figure 1, SEM images of the surfaces of the Lei Pos after the DCB solution is soaked are shown in figure 2, and according to figures 1-2, the DCB solution can remove iron films (YS) formed in the natural growth process of the Lei Pos and does not damage plant roots.
3. Planting the cleaned Leersia hexandra into the plant culture solution which is obtained in the step 1 and does not contain Fe and KH 2PO4, wherein the adding amount of the plant culture solution is 20 mL/plant, and culturing for 12-24 h.
4. FeSO 4·7H2 O was added to the plant culture solution obtained in step 1 (2) and containing no Fe and KH 2PO4, and the amount of FeSO 4·7H2 O added as the exogenous Fe (II) was 25mg/L, namely, 25mg of FeSO 4·7H2 O per L of the plant culture solution containing no KH 2PO4 was added and was denoted as Fe25. After FeSO 4·7H2 O is added, the pH of the solution is regulated to 5.9-6.1 by 0.1mol/L NaOH again, and the solution is cultured for 2-3 days to induce the root surface to form an iron film rapidly.
5. After the formation of the iron film, transferring the induced and cultivated Lei grass into the plant culture solution which is obtained in the step 1 (3) and does not contain any valence state Fe for 12-24 hours, and removing the unstable Fe phase on the root surface.
Example 2
The difference in example 1 is that the exogenous addition amount of FeSO 4·7H2 O in step 4 is 30mg/L, which is denoted as Fe30.
Example 3
The difference in example 1 is that the exogenous addition amount of FeSO 4·7H2 O in step 4 is 40mg/L, which is denoted as Fe40.
Example 4
The difference in example 1 is that the exogenous addition amount of FeSO 4·7H2 O in step 4 is 50mg/L, which is denoted as Fe50.
Example 5
The difference in the same manner as in example 1 is that the exogenous addition amount of FeSO 4·7H2 O in step 4 was 60mg/L, which was designated as Fe60.
Example 6
The difference in example 1 is that the exogenous addition amount of FeSO 4·7H2 O in step 4 is 100mg/L, which is referred to as Fe100.
Comparative example 1
The difference is that the exogenous addition amount of FeSO 4·7H2 O in step 4 was 0mg/L, which was designated as Fe0, as in example 1.
Comparative example 2
The difference from example 1 is that the formulation of the DCB solution in step 1 (1) is as follows in Table 5:
TABLE 5DCB solution formulation
| Compounds of formula (I) | Concentration of |
| Na3C6H5O7·2H2O | 0.015mol/L |
| NaHCO3 | 0.0625mol/L |
| Na2S2O4 | 0.10mol/L |
| Deionized water | Allowance of |
The DCB solution obtained in table 5, after soaking, can remove iron films (YS) formed during natural growth of the young standing grain, but can damage plants.
Comparative example 3
The difference from example 1 is that the formulation of the DCB solution in step 1 (1) is as follows in Table 6:
TABLE 6DCB solution formulation
| Compounds of formula (I) | Concentration of |
| Na3C6H5O7·2H2O | 0.0006mol/L |
| NaHCO3 | 0.0061mol/L |
| Na2S2O4 | 0.004mol/L |
| Deionized water | Allowance of |
The Leersia hexandra Litsea solution obtained in Table 6 after soaking could not effectively remove the iron film formed during the natural growth of Leersia hexandra.
Test example 1
After the induction of the iron films of examples 1 to 6 and comparative example 1 was completed, the iron film on the surface of the root of Leersia hexandra with DCB solution was extracted, and the Fe content of the iron film under different treatments was analyzed by Flame Atomic Absorption Spectrometry (FAAS). The root system after DBC extraction is washed three times by deionized water, dried for 48 hours at 70 ℃ until the weight is constant, and then weighed and recorded. The experimental results are shown in table 7 and fig. 3.
TABLE 7 Fe content in iron films obtained by different treatments
| Treatment mode | Fe content (g/kg, FW) |
| Fe25 | 13.44±1.69c |
| Fe30 | 13.89±1.71c |
| Fe40 | 19.18±1.93b |
| Fe50 | 20.01±0.95b |
| Fe60 | 21.88±1.22b |
| Fe100 | 29.32±1.98a |
| Fe0 | 3.97±0.59d |
| YS | 20.86±2.05b |
Note that: YS is the Fe content in the naturally growing Lishi grass root surface iron film, FW represents fresh weight, and the data of different letters in the same column represent significant difference (p is less than 0.05).
From the results shown in Table 7 and FIG. 3, it can be seen that the iron content in the iron film gradually increases with the increase of the content of the exogenous Fe (II), and that the content of Fe in the iron film is similar to that in the naturally-grown Lei-Po root surface iron film (YS) when the exogenous Fe (II) of example 4 is added in an amount of 50 mg/mL.
Test example 2
After the formation of the iron film, the SOD, POD and CAT activity indexes of the root system of the naturally grown Leersia hexandra (denoted as YS) of example 4, comparative example 1 and the naturally grown Leersia hexandra were measured by using a biological kit built in Nanjing, the physiological activity of the root system of the Leersia hexandra was reflected, and the results are shown in table 8.
TABLE 8 antioxidant enzyme Activity of Leersia hexandra root systems under different treatments
| Treatment mode | SOD(U/g，FW) | POD(U/g，FW) | CAT(U/g，FW) |
| YS | 164.64±10.78a | 210±7.05b | 10.57±1.41a |
| Fe0 | 172.03±9.62a | 222.33±3.75ab | 11.11±3.38a |
| Fe50 | 168.67±5.31a | 225.17±9a | 11.38±0.81a |
Note that: data represent mean ± standard deviation (n=3), FW represents fresh weight, and data with different letters in the same column represent significant differences (p < 0.05).
According to Table 8, it can be seen that apart from slightly floating POD activity, the difference between SOD and CAT is not obvious, and the root surface iron film rapid induction method of the invention does not cause physiological damage to Leersia hexandra root systems.
Test example 3
Adding 10mg/L of Cr (VI) (K 2Cr2O7) into the plant culture solution obtained in the step (1) to obtain a culture solution, and respectively planting the Leersia hexandra induced and cultured in the example 4, the Leersia hexandra induced and cultured in the comparative example 1 and the naturally grown Leersia hexandra into the culture solution, wherein the culture solution is sequentially marked as Fe50Cr10, fe0Cr10 and YSCr; naturally grown Leersia hexandra (L.) Heim is planted in the plant broth obtained in step 1 (1) (i.e., without the addition of chromium stress), designated YSCr0.
The culture solution was changed every 3d during the culture of Fe50Cr10, fe0Cr1, YSCr, and YSCr0, the pH of the culture solution was adjusted to 5.9-6.1 with 0.1M NaOH before each culture, the pH was not adjusted during the culture, and the total chlorophyll content in the leaves of Lei's Poa were measured per 3d sample according to spectrophotometry for determination of chlorophyll content in fruits, vegetables and their products, NY/T3082-2017, and the results are shown in Table 9 and FIG. 4.
TABLE 9 Total chlorophyll content in Liriope grass leaves in different culture modes
Note that: data represent mean ± standard deviation (n=3), FW represents fresh weight, and data with different letters in the same column represent significant differences (p < 0.05).
Cr (VI) has remarkable inhibition effect on photosynthesis, and plant accumulated chromium can reduce growth, so that new leaves yellow, and chloroplast ultrastructure is changed. As can be seen from table 9 and fig. 4, the chlorophyll content in the young grass blades not subjected to chromium stress was also slowly increasing over time, and the chlorophyll content of the Leersia hexandra in each treatment under the stress of chromium is obviously reduced. Especially, compared with Lei Po with iron film not attached to root surface, the chlorophyll content is reduced by 23.3% before chromium stress, and when the addition amount of exogenous Fe (II) in example 4 is 50mg/mL, the chlorophyll content is reduced by 15.5%, and the presence of the iron film on root surface under chromium stress has a certain protection effect on Lei Po.
Test example 4
The Lei Pos induced-cultured in examples 1, 4 and 6, the Lei Pos induced-cultured in comparative example 1 and the naturally grown Lei Pos were respectively planted in a plant culture solution containing 10mg/L Cr (VI) (K 2Cr2O7), and were designated as Fe25Cr10, fe50Cr10, fe100Cr10, fe0Cr10 and YSCr in this order; the YS group without chromium stress was used as a control and was designated YSCr0.
After each treatment group is treated for 9d, the Leersia hexandra is harvested, the roots and overground parts are cut off and separated by scissors, a part of root systems are extracted by DCB solution to obtain root surface iron films, the chromium content in the extracting solution is measured by FAAS, and the chromium content in the Leersia hexandra root surface iron films under different treatments is determined, and the results are shown in Table 10 and FIG. 5;
TABLE 10 chromium content in Leersia hexandra root surface iron films under different treatments
| Group of | Chromium content (mg/kg, FW) |
| YSCr10 | 487.82±41.42 |
| Fe0Cr10 | 325.16±32.7 |
| Fe25Cr10 | 434.11±87.44 |
| Fe50Cr10 | 649.25±67.44 |
| Fe100Cr10 | 788.06±57.43 |
Note that: data represent mean ± standard deviation (n=3), FW represents fresh weight, and data with different letters in the same column represent significant differences (p < 0.05).
Collecting overground parts and leached roots, measuring the chromium content in different treated Leersia hexandra tissues by adopting a flame atomic absorption assay method after digestion, and calculating a transport coefficient (TF, the ratio of the chromium concentration of the overground parts of plants to the root system). The results are shown in Table 11.
TABLE 11 chromium content and transport coefficient in different treated Leersia hexandra tissues
Note that: data represent mean ± standard deviation (n=3), DW represents dry weight, and data from the same column with different letters represent significant differences (p < 0.05).
As can be seen from tables 10 to 11 and fig. 5, the Lei's grass having the iron film attached to the root system adsorbed more chromium than the Lei's grass having no iron film attached thereto, and the adsorbed chromium increased with the increase of the addition amount of Fe (II) during the induction. Under the condition that the total Fe of the iron film is similar, the adsorbed chromium content of the iron film treated by Fe50Cr10 is 133 percent of YSCr, and the method for providing the iron film can adsorb more chromium on the surface than the iron film grown in natural environment; as can be seen from comparison of transport coefficients, compared with the iron film formed in the natural growth process, the iron film formed by induction of the invention can transfer more chromium from the root system of Leersia hexandra to the aerial part of the Leersia hexandra, and the transport coefficient is obviously higher than YSCr when the addition amount of exogenous Fe (II) in the embodiment 4 is 50 mg/mL.
The method provided by the invention can not cause physiological damage to the root system of the Leersia hexandra in the induction process of the iron film, and the quantity (thickness) of the iron film is increased along with the increase of exogenous Fe (II). After the iron film is formed on the root surface of the Leersia hexandra, the damage of Cr (VI) to photosynthesis of the Leersia hexandra can be reduced, and meanwhile, the iron film formed by induction can adsorb more chromium in the environment, remarkably improve the chromium content of the overground part of the Leersia hexandra, and improve the capability of the Leersia hexandra in repairing chromium polluted water body.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A method for improving the restoration of heavy metal chromium polluted water bodies by super-enriched plant Leersia hexandra, which is characterized by comprising the following steps: culturing and pretreating Lestus by using a plant culture solution which does not contain Fe and KH 2PO4 for 12-24 hours; mixing the plant culture solution without Fe and KH 2PO4 with exogenous ferrous ions, and inducing and culturing the pretreated Leersia hexandra root surface to generate an iron film.
2. The method of claim 1, wherein the concentration of exogenous ferrous ions is 25-100 mg/L;
the time of the induction culture is 2-3 d; the initial pH value of the induction culture is 5.9-6.1.
3. The method according to claim 1, wherein the induction culture comprises light culture and dark culture, the temperature of the light culture is 30 ℃, the temperature of the dark culture is 20 ℃, and the time of the light culture is 12-14 h/d.
4. The method of claim 1, wherein prior to the induction culture, further comprising: cleaning the Leersia hexandra root surface by adopting a DCB solution.
5. The method of claim 4, wherein the DCB solution comprises 0.003mol/L Na3C6H5O7·2H2O,0.0125mol/L NaHCO3、0.020mol/L Na2S2O4 and the balance water.
6. The method according to any one of claims 1 to 5, wherein the plant culture solution free of Fe and KH 2PO4 consists of ：5mmol/L Ca(NO3)2·4H2O、5mmol/L KNO3、2mmol/L MgSO4·7H2O、0.3μmol/L CuSO4·5H2O、0.045mmol/L H3BO3、0.01mmol/L MnCl2·4H2O、0.8μmol/L ZnSO4·7H2O、0.1μmol/L NaMoO4·2H2O、0.02mmol/L Na2-EDTA as the following concentration components and the balance water.
7. The method of claim 6, wherein the pH of the Fe and KH 2PO4 free plant broth is 5.9 to 6.1.
8. The method of claim 1, further comprising, after the induction culture is completed: culturing Lestus by using a plant culture solution without Fe for 12-24 hours.
9. The method of claim 8, wherein the Fe-free plant broth consists of ：5mmol/L Ca(NO3)2·4H2O、5mmol/L KNO3、2mmol/L MgSO4·7H2O、1mmol/L KH2PO4、0.3μmol/L CuSO4·5H2O、0.045mmol/L H3BO3、0.01mmol/L MnCl2·4H2O、0.8μmol/L ZnSO4·7H2O、0.1μmol/L NaMoO4·2H2O、0.02mmol/L Na2-EDTA and the balance water in the following concentrations of components.
10. The method of claim 9, wherein the pH of the Fe-free plant broth is 5.9-6.1.
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