CN113351642A - Repair method for repairing antimony and zinc combined pollution and application - Google Patents
Repair method for repairing antimony and zinc combined pollution and application Download PDFInfo
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Images
Classifications
-
- 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
- B09C2101/00—In situ
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Mycology (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a remediation method for remedying antimony and zinc combined pollution and application thereof, and particularly relates to the field of soil remediation. The repairing method comprises the steps of enrichment of sulfate reducing bacteria, solidification of sulfate reducing flora on Sb (III) and Zn (II) and acute toxicity detection. The microbial method provided by the invention is used for treating the antimony-zinc composite pollution, not only is the cost low and the efficiency high, but also harmful pollutants in the environment can be treated in situ, and thus the sustainable development of the environment is realized. The microorganism has stronger metabolic capability, large specific surface area and charged surface, so the microorganism can repair heavy metal pollution through cell metabolism, biological adsorption, precipitation and redox. The sulfate reducing flora provided by the invention can simultaneously convert Sb (III) and Zn (II) into sulfide precipitates, change the free form of Sb (III) and Zn (II) into insoluble precipitates, reduce the degree of environmental pollution, provide a bioremediation material for the remediation of heavy metal pollution of mines, and have good industrial application prospects.
Description
Technical Field
The invention relates to the field of soil pollution treatment, in particular to a remediation method for remedying antimony and zinc combined pollution and application thereof.
Background
Heavy metals are potentially harmful pollutants, mainly come from mining and smelting and other industries, life, agriculture, transportation and the like, and 40% of heavy metal pollution comes from the non-ferrous metal mine industry. China has the most abundant antimony (Sb) resource in the world, and is mainly concentrated in Guangxi, Hunan, Yunnan and the like. The tin mine in the middle of Hunan province is the world's largest antimony ore, called "world antimony city". Sb is an indispensable element in modern industry, and the widespread use of mining, smelting, coal burning, and Sb-containing products causes a large amount of Sb pollutants to enter the environment. Most mine environments are often in composite pollution of Sb and various heavy metals, have the characteristics of accumulativeness, sustainability, concealment and the like, enter soil, water and atmosphere through various modes, can migrate and circulate in an ecological system, and finally possibly enter human bodies to harm the health of human beings. If the Sb powder is used in places containing Sb dust for a long time, respiratory tract, cardiac muscle and liver of people can be infected, and even the Sb powder is carcinogenic at high concentration and endangers life. The United States Environmental Protection Agency (USEPA) and the European Union (EU) have listed Sb and Sb-containing compounds as priority pollutants. Therefore, the composite pollution of Sb and various heavy metals in mine environment becomes a great environmental problem which needs to be solved urgently in the world nowadays.
The method for restoring heavy metal pollution in a mining area mainly comprises a physical method, a chemical method and a biological method for restoring through plants, animals and microorganisms. The physical method and the chemical method for repairing the heavy metal pollution in the mining area have higher repairing cost, long repairing period and certain limitation. In addition, physical and chemical remediation methods are easy to cause secondary pollution, and cannot achieve a sustainable environment remediation effect, so that the remediation of the antimony-zinc composite soil is difficult.
Bioremediation is the use of biological entities or components that are naturally occurring or artificially created to remediate various environmental pollutants. The cost is low, the treatment efficiency is high, and the environment harmful pollutants with lower concentration can be treated in situ. Bioremediation has great potential in the treatment of polluted environment, and can coordinate the relationship between economic development and environmental protection, thereby realizing the sustainable development of society. However, the existing microorganism remediation of the heavy metal pollution in the mining area generally adopts single antimony or zinc for remediation, and cannot achieve simultaneous remediation of antimony-zinc composite pollution.
Disclosure of Invention
Therefore, the invention provides a repairing method for repairing antimony and zinc composite pollution and application thereof, and aims to solve the problems that the existing antimony and zinc pollution treatment cost is high, and the antimony and zinc composite pollution cannot be repaired at the same time.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to an aspect of the present invention, there is provided a repairing method for repairing antimony and zinc composite contamination, the method comprising the steps of:
step one, enrichment of sulfate reducing bacteria
Inoculating the mine sample into a reactor for enriching the culture medium, and adding Fe (NH) into the culture medium4)2·(SO4)2·6H2Filling nitrogen into the reactor to discharge oxygen in the reactor, sealing a bottle cap and culturing in an incubator; after the liquid turns black and the liquid turns black as well as is detected by lead acetate test paper, opening the bottle mouth to smell obvious smelly eggs, inoculating and domesticating the eggs by using the same enrichment medium to obtain original sulfate reducing flora; continuously culturing the original sulfate reducing bacteria until logarithmic growth phase to obtain activated original sulfate reducing bacteria flora in logarithmic growth phase;
step two, solidifying Sb (III) and Zn (II) by sulfate reducing flora
Firstly, simultaneously adding 10mg/L of Sb (III) and Zn (II) into an SZ reactor, and adding 10mg/L of Sb (III) into an SS reactor; zn (II) is added into the ZZ reactor at a concentration of 10 mg/L; taking a flora of an activated original sulfate reducing flora in logarithmic growth phase, inoculating the flora into a reactor in an inoculation amount of 10%, introducing nitrogen to remove oxygen, plugging the reactor with a rubber stopper, and culturing in an incubator; after the experiment is finished, measuring the concentration change of Sb (III) and Zn (II) in the reactor within 5 days by using an inductively coupled plasma emission spectrometer, and identifying the composition of a compound in the precipitate by combining a scanning electron microscope and an EDS (electron-dispersive spectroscopy) spectrogram;
step three, acute toxicity detection
The single toxicity and mixed toxicity of Sb (III) and Zn (II) after the treatment of the sulfate reducing bacteria are detected by the inhibition rate of the luminescence of the vibrio fischeri.
Further, the formula of the enrichment medium is K2HPO4 0.5 g/L、Na2SO4 1g/L、MgSO4·7H2O 2g/L、CaCl2·6H2O 0.1g/L、NH4Cl 1g/L, yeast extract 1g/L, sodium lactate 1g/L and ascorbic acid 0.5 g/L.
Further, the pH of the enrichment medium is 7.0 +/-0.2.
Further, said Fe (NH)4)2·(SO4)2·6H2The O concentration was 0.5 g/L.
Further, in the first step, the culture condition in the incubator is 30 ℃ incubator static culture for 5 days.
Further, in the first step, the inoculation acclimatization method is to perform inoculation acclimatization 5 times with an inoculation amount of 10%.
Further, in the second step, the culture condition in the incubator is 30 ℃ incubator static culture for 5 days.
The repairing method for repairing antimony and zinc combined pollution provided by the invention can be applied to bioremediation of heavy metal pollution of mines.
The invention has the following advantages:
the microbial method provided by the invention is used for treating the antimony-zinc composite pollution, not only is the cost low and the efficiency high, but also harmful pollutants in the environment can be treated in situ, and thus the sustainable development of the environment is realized. The microorganism has stronger metabolic capability, large specific surface area and charged surface, so the microorganism can repair heavy metal pollution through cell metabolism, biological adsorption, precipitation and redox.
The sulfate reducing flora provided by the invention can simultaneously convert Sb (III) and Zn (II) into sulfide precipitates, change the free form of Sb (III) and Zn (II) into insoluble precipitates, reduce the degree of environmental pollution, provide a bioremediation material for the remediation of heavy metal pollution of mines, and have good industrial application prospects.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 is a scanning electron micrograph of sulfate-reducing bacteria provided by the present invention;
FIG. 2 is a graph showing the results of the reaction in the reactor used in the experiment of the present invention after 5 days;
FIG. 3 is a graph showing the total Sb and Zn concentration variations in different reactors according to the present invention;
FIG. 4 shows the product identification in the reactor provided by the present invention, (a) is a scanning electron micrograph, and (b) is an EDS energy spectrum;
FIG. 5 is an XRD pattern of the precipitate in the SZ reactor after the microbial treatment provided by the invention;
FIG. 6 shows the variation of TOC and pH in a bioreactor provided by the present invention;
FIG. 7 is a composition of microbial communities in different reactors provided by the present invention, wherein a is a phylum level and b is a genus level;
FIG. 8 is a graph illustrating toxicity testing in a reactor after microbial treatment according to the present invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
SS represents single Sb contamination
ZZ stands for single Zn contamination
SZ represents composite Sb and Zn contamination
Example 1A remediation method for remediating antimony and zinc combined pollution
1. Enrichment and domestication of sulfate reducing bacteria
The enrichment medium formula comprises: k2HPO4 0.5 g/L、Na2SO4 1 g/L、MgSO4·7H2O 2g/L、CaCl2·6H2O 0.1g/L、NH4Cl 1g/L, yeast extract 1g/L, sodium lactate 1g/L, ascorbic acid 0.5 g/L; the pH was 7.0. + -. 0.2.
1g of the mine sample was weighed into a reactor containing 100mL of enrichment medium and 0.5g/LFe (NH) was added to the medium4)2·(SO4)2·6H2And O, filling nitrogen into the reactor for 5min to discharge oxygen in the reactor, sealing the bottle cap, and standing and culturing for 5 days in an incubator at 30 ℃. Opening the bottle mouth to smell obvious smelly egg smell after the liquid turns black and the same blackening is detected by lead acetate test paper, which indicates that the bottle mouth has H2S gas is generated, and at the moment, the sulfate-reducing bacteria group is greatly propagated. The same medium was used for 5 acclimations at an inoculum size of 10% to obtain the original sulfate-reducing flora. Observing the morphology of the sulfate reducing bacteria by a scanning electron microscopeThe body is in the shape of a short rod, as shown in fig. 1.
2. Evaluation of solidification Capacity of sulfate-reducing groups for Sb (III) and Zn (II)
Firstly, 10mg/L of Sb (III) and Zn (II) are added into an SZ reactor at the same time, and 10mg/L of Sb (III) and Zn (II) are added into an SS reactor and a ZZ reactor respectively. Taking flora in logarithmic phase, inoculating 10% of the flora into a reactor, introducing nitrogen, plugging a rubber stopper, and placing the rubber stopper into an incubator at 30 ℃ for reaction. The control reactor was charged with Sb (III) and Zn (II) at the same concentrations as "SZ" and inoculated with the inactivated flora in a proportion of 10%, the reaction period being 5 days, otherwise identical to the bioreactor. After the experiment was completed, it was clearly seen that a very clear solid material appeared at the bottom of each bioreactor, a dark orange-red precipitate was observed at the bottom of the SS reactor, an off-white precipitate appeared in ZZ, and a light yellow precipitate appeared in SZ, as shown in fig. 2. In addition, the concentration changes of Sb (III) and Zn (II) in the reactor within 5 days are measured by an inductively coupled plasma emission spectrometer, and the result shows that the total concentration of Sb and Zn in the SZ, SS and ZZ reactors is obviously reduced as shown in figure 3, which shows that the enriched and domesticated sulfate reducing flora can synchronously fix Sb (III) and Zn (II), and provides possibility for the synchronous fixation of the composite pollution of heavy metals in the mine environment.
3. Acute toxicity detection
The toxicity of the substance can be illustrated by the inhibition rate of the Vibrio fischeri luminescence by using the single toxicity and the mixed toxicity of Sb (III) and Zn (II) under the treatment of the Vibrio fischeri on the sulfate reducing bacteria. Before the experiment is started, the luminescence effects of the deionized water and the culture medium used in the experiment are firstly detected, the luminosity expressed by the deionized water and the culture medium through the Vibrio fischeri is the same, and the luminescence effect produced by the culture medium is used as a contrast in the experiment. As can be seen from FIG. 8, the inhibition rates of the heavy metals in the reactors to Vibrio fischeri show a gradual decrease trend along with the change of time, the inhibition rates in the three reactors are not very different, the inhibition rate in SZ is decreased from 71.87% to 4.30% from the beginning, the inhibition rates in SS and ZZ reactors are decreased from 64.58% and 62.50% to 2.83% and 0.27% respectively, and the enriched sulfate reducing bacteria are used for forming precipitates of Sb (III) and Zn (II) to reduce the concentrations of the Sb (III) and Zn (II) and gradually reduce the environmental toxicity in the process of synchronously fixing the Sb (III) and Zn (II), so that the method is an environment-friendly repairing method.
Experimental example 1 identification of reaction product
After the end of one reaction cycle, the precipitate in SZ was collected and characterized after centrifugation and drying. FIG. 4(a) is a scanning electron micrograph of the microorganisms, which does not show a clear short rod shape compared to FIG. 1, and is entirely covered with a layer, presumably covered with a colony of bacteria that may have formed. Referring to FIG. 4(b) and Table 1, it can be seen that the reaction product is mainly composed of C, O, S, P, Cl, Na, Mg, Sb, Zn, etc., wherein C, O, P is present because of organic substances in bacterial cells, Cl, Na, Mg is present probably due to the culture medium of microorganisms, and S and Zn, Sb are present probably because Sb (III) and Zn (II) are fixed as sulfide precipitates. To further verify this hypothesis, the precipitate generated in the SZ reactor was analyzed in conjunction with XRD. As shown in FIG. 5, Sb is 17.54 °, 37.08 °, 47.18 ° and 60.55 °2S3Characteristic peak of (PDF card number 01-0538); the characteristic peaks of ZnS (01-0677 in PDF card) at 28.68 degrees, 39.67 degrees, 56.78 degrees and 78.30 degrees show that the precipitates generated in the research are mainly composed of sulfides, namely Sb2S3And ZnS, in the form.
TABLE 1 element ratios in EDS
Experimental example 2 analysis of changes in pH and TOC in a reactor
The TOC value in the reaction process is detected by a total organic carbon analyzer, and the pH in the reaction process is detected by a pH meter. As shown in FIG. 6, the TOC concentration gradually decreased over the first three days and slowly stabilized thereafter, indicating that sodium lactate acts as an electron donor and carbon source during microbial sulfate ion immobilization of Sb (III) and Zn (II), as also shown in previous studies. The pH value of the solution is firstly reduced, then slowly increased and finally gradually stabilized at about 6.5, which shows that the pH value after reaction is finally stabilized at a neutral condition and cannot cause an extreme acid-base environment.
Experimental example 3 evolution of microbial community architecture within a reactor
Fig. 7(a) is the microbial community composition of the reactor at the portal level, with significant changes in the microbial composition of the sulfate-reducing community during the immobilization of Sb (iii) and Zn (ii). Proteobacteria (Proteobacteria), Firmicutes (Mycobactes) and Bacteroidota (Bacteroides) were dominant bacteria in the original sulfate-reducing bacteria group (Control), with abundances of 14.8%, 78.76% and 4.81%, respectively. Wherein Proteobacteria and Firmicutes are dominant bacteria in all three bioreactors, whereas Desulfobacterota is less abundant in all bioreactors. Both Proteobacteria and Firmicutes were significantly increased in abundance in the composite contaminated (SZ) reactor compared to the control, 52.83% and 46.23%, respectively. Proteobacteria and Firmicutes have been reported to have been found extensively in the anaerobic sulfate-reduction remediation of wastewater. The abundance of bacteroideta in single Sb (iii) (SS) and single Zn (ii) (ZZ) contaminations was 18.64% and 27.49%, respectively, but almost zero in composite contaminations (SZ), suggesting that bacteroidata phyla may have an important role in the immobilization of Sb (iii) and Zn (ii) alone.
FIG. 7(b) shows the microbial composition in each bioreactor at the genus level. The results show that the addition of heavy metals has a great influence on the composition of the original sulfate-reducing flora. The Clostridium genus was significantly reduced in abundance in all three reactors with heavy metals added, compared to the control, probably due to the growth inhibition of the genus by the addition of heavy metals. Zhang et al, who have been identified as Clostridium (Clostridium) by enriching sulfate-reducing bacteria from a stream, can effectively reduce Sb (V) to Sb (III) and form Sb2S3Precipitation, according to the experimentThe conclusions are inconsistent. Acinetobacter is remarkably increased in three reactors added with heavy metals, particularly as high as 36.84% in SZ, and has been reported to be detected in Sb-polluted environments, and many researches find that the Acinetobacter can oxidize Sb (III), and the Acinetobacter possibly has an important role in the geochemical process of Sb. Furthermore, dysgenomonas showed a significant increase in SS and ZZ (17.17%, 27.14%), Citrobacter was significantly enriched in all three heavy metal supplemented reactors (14.13% SZ, 29.86% SS, 22.19% ZZ). The abundances of Anaerostinum and Tuzzerella are both increased significantly in SZ, and are 12.66% and 13.74%, respectively, so Anaerostinum and Tuzzerella may also play an important role in the simultaneous immobilization of Sb (III) and Zn (II).
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A remediation method for remediating antimony and zinc combined pollution, comprising the steps of:
step one, enrichment of sulfate reducing bacteria
Inoculating the mine sample into a reactor for enriching the culture medium, and adding Fe (NH) into the culture medium4)2·(SO4)2·6H2Filling nitrogen into the reactor to discharge oxygen in the reactor, sealing a bottle cap and culturing in an incubator; after the liquid turns black and the liquid turns black as well as is detected by lead acetate test paper, opening the bottle mouth to smell obvious smelly eggs, inoculating and domesticating the eggs by using the same enrichment medium to obtain original sulfate reducing flora; continuously culturing the original sulfate reducing bacteria until logarithmic growth phase to obtain activated original sulfate reducing bacteria flora in logarithmic growth phase;
step two, solidifying Sb (III) and Zn (II) by sulfate reducing flora
Firstly, simultaneously adding 10mg/L of Sb (III) and Zn (II) into an SZ reactor, and adding 10mg/L of Sb (III) into an SS reactor; zn (II) is added into the ZZ reactor at a concentration of 10 mg/L; taking an activated original sulfate reducing flora in logarithmic growth phase, inoculating the activated original sulfate reducing flora into a reactor in an inoculation amount of 10%, introducing nitrogen to remove oxygen, plugging a rubber stopper, and culturing in an incubator; after the experiment is finished, measuring the concentration change of Sb (III) and Zn (II) in the reactor and the composition of compounds in the sediment within 5 days by using an inductively coupled plasma emission spectrometer;
step three, acute toxicity detection
The single toxicity and mixed toxicity of Sb (III) and Zn (II) after the treatment of the sulfate reducing bacteria are detected by the inhibition rate of the luminescence of the vibrio fischeri.
2. The repairing method for composite pollution of antimony and zinc as claimed in claim 1, wherein the formula of said enrichment medium is K2HPO40.5g/L、Na2SO41g/L、MgSO4·7H2O 2g/L、CaCl2·6H2O 0.1g/L、NH4Cl 1g/L, yeast extract 1g/L, sodium lactate 1g/L and ascorbic acid 0.5 g/L.
3. The remediation method of claim 1, wherein the pH of the enrichment medium is 7.0 ± 0.2.
4. The repairing method for repairing antimony and zinc combined pollution according to claim 1, characterized in that Fe (NH)4)2·(SO4)2·6H2The O concentration was 0.5 g/L.
5. The repairing method for repairing antimony and zinc combined pollution according to claim 1, wherein in the first step, the culture condition in the incubator is 30 ℃ incubator static culture for 5 days.
6. The method for remediating antimony and zinc combined pollution as recited in claim 1, wherein in the first step, the inoculation acclimatization method is implemented for 5 times by inoculating and acclimatizing 10% of the inoculation amount.
7. The repairing method for repairing antimony and zinc combined pollution according to claim 1, wherein in the second step, the culture condition in the incubator is 30 ℃ incubator static culture for 5 days.
8. The remediation method for remediation of combined antimony and zinc pollution according to any one of claims 1 to 7 can be applied to bioremediation of heavy metal pollution in mines.
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