CN107641608A - A kind of manganese oxide minerals and its application - Google Patents

A kind of manganese oxide minerals and its application Download PDF

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Publication number
CN107641608A
CN107641608A CN201611155703.7A CN201611155703A CN107641608A CN 107641608 A CN107641608 A CN 107641608A CN 201611155703 A CN201611155703 A CN 201611155703A CN 107641608 A CN107641608 A CN 107641608A
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manganese oxide
salmonella
solid matrix
water body
bacterium sample
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CN107641608B (en
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孟佑婷
郑洁
尚宏忠
杨素玲
刘桂君
王平
周思静
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BEIJING RADIATION CENTER
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BEIJING RADIATION CENTER
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Abstract

The present invention relates to a kind of manganese oxide minerals and its application.The manganese oxide minerals are dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217, and its deposit number is CGMCC NO 13235.The bacterium can be by Mn (II) synthesising biological manganese oxide in water body or solid matrix.Have a extensive future.

Description

A kind of manganese oxide minerals and its application
Technical field
The present invention relates to the application of a kind of manganese oxide minerals and its synthesising biological manganese oxide.Specifically, the manganese oxidation Bacterium is dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217, and its deposit number is:CGMCC NO 13235.
Background technology
Manganese is the transition metal of abundance second in the earth's crust, is widely present in nature.Manganese oxide is important in environment Adsorbent, oxidant and catalyst.Microorganism can generate oxide with catalysis oxidation Mn (II), can make Mn (II) oxidation speed Rate improves several orders of magnitude.Microorganism can aoxidize Mn (II) by enzymatic reaction or change environmental condition.Biological oxidation manganese leads to It is often the nanoparticle of big specific surface area, amorphous state or shortrange order.
The manganese oxide minerals reported at present are distributed mainly on Firmicutes (Firmicutes), the high G+C of low G+C contents The actinomyces door (Actinobacteria) of content and the α of Proteobacteria (Proteobacteria)-, β-and γ-mycetozoan Subclass.The type strain of research mainly has the bacillus SG1 (Bacillus) of Firmicutes, Proteobacteria α-deformation Gammaproteobacteria The fine quotation silk bacterium SS-1 of pseudomonas putida MnB1/GB-1 (Pseudomonas putida) and β-deformation Gammaproteobacteria (Leptothrix discophora)。
The content of the invention:
The present invention provides a kind of application of manganese oxide minerals and its synthesising biological manganese oxide.
In a first aspect, the present invention provides a kind of manganese oxide minerals, the manganese oxide minerals are dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217, the bacterial strain are preserved in Chinese microorganism strain preservation pipe on November 3rd, 2016 Reason committee common micro-organisms center (CGMCC, No. 3 Chinese Academy of Sciences microorganisms of city of BeiJing, China Chaoyang District North Star West Road 1 institute Research institute, postcode:100101), its deposit number is CGMCC NO 13235.
The dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 are old from Changping District, Beijing manganese ore The soil of location, through screening, separating, purifying and obtain.Dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 are blue for leather Family name's negative bacillus.Circular petite white in solid medium, surface is smooth.Rod-short bacterium is presented under ESEM, It is long 0.6-1.2 μm, it is wide 0.2-0.4 μm.The i.e. dynamic glue bacterium sample Shen Salmonella Shinella of manganese oxide minerals of the present invention Zoogloeoides CP217 have Mn (II) oxidation activity in pH value 5.0-8.0, and at 20-30 DEG C there is Mn (II) to aoxidize Activity.Simultaneously synthesising biological manganese oxide can be grown under Mn (II) concentration not higher than 40mM.
Dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 16S rDNA sequences are imported NCBI's GenBank databases carry out sequence analysis, the results showed that, maximum similar strain is Shinella zoogloeoides, similar Degree 99%.It may determine that the bacterial strain belongs to Shinella zoogloeoides, name:Dynamic glue bacterium sample Shen Salmonella.Therefore, by this Strain Designation is dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217.Shinella zoogloeoides CP217 16S rDNA sequences are shown in SEQ ID No:Shown in 1.
Second aspect, the present invention also provide the manganese oxide minerals Shinella zoogloeoides CP217 and are used to close Into the application of biological oxidation manganese.The i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides of manganese oxide minerals of the present invention CP217 can be used for the synthesis of biological oxidation manganese in water body and solid.Specific method is, by Shinella zoogloeoides CP217 is inoculated into the water body or solid matrix containing Mn (II), and at 20-30 DEG C, pH value is cultivated under conditions of being 5.0-8.0. Incubation time is related to nutritional ingredient in microbial activity and water body, general to be no less than 7 days.The Shinella The temperature that zoogloeoides CP217 are cultivated in water body is 20-30 DEG C, and optimum temperature is 30 DEG C, and pH value is pH 5.0- 8.0, optimal pH pH6.0.Mn (II) concentration is not higher than 40mM (such as 1-40mM) in water or in solid matrix, preferably not Higher than 30mM, optimal is 20mM.
The third aspect, the present invention provide a kind of method of synthesising biological manganese oxide, and methods described comprises the steps:It incite somebody to action this The i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of invention manganese oxide minerals or its microbial inoculum or the training containing the bacterium Nutrient solution is added in water body or solid matrix, and at 20-30 DEG C, pH value cultivates appropriate time under conditions of being 5.0-8.0.During culture Between it is different because of activity when bacterium is added and the condition of matrix, generally no greater than 7 days.The Shinella zoogloeoides The temperature that CP217 is cultivated in water body is 20-30 DEG C, and optimum temperature is 30 DEG C, pH value pH5.0-8.0, and optimal pH is pH6.0.Mn (II) concentration is not higher than 40mM (such as 1-40mM), preferably no greater than 30mM in water or in solid matrix, optimal For 20mM.
Fourth aspect, the present invention provides a kind of removal water body or the method for the Mn (II) in solid matrix, including this is sent out The i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of bright manganese oxide minerals or its microbial inoculum or the culture containing the bacterium Liquid is added in water body or solid matrix, and appropriate time is cultivated under conditions of 20-30 DEG C, pH 5.0-8.0.Incubation time because Activity and the condition of matrix when bacterium is added and it is different, generally no greater than 7 days.The Shinella zoogloeoides The temperature that CP217 is cultivated in water body is 20-30 DEG C, and Optimal Temperature is 30 DEG C, pH value pH5.0-8.0, and optimal ph is pH6.0.Mn (II) concentration is not higher than 40mM (such as 1-40mM), preferably no greater than 30mM in water or in solid matrix, optimal For 20mM.
Manganese oxide minerals of the present invention can be applied, which to carry out the water body that synthesising biological manganese oxide or progress Mn (II) are removed, to be included But it is not limited to industrial wastewater, sanitary wastewater, underground water or running water.Manganese oxide minerals of the present invention can be applied to carry out synthesising biological The solid matrix that manganese oxide or progress Mn (II) are removed includes but is not limited to soil, deposit etc..Mn in water or in solid matrix (II) concentration is not higher than 40mM (such as 1-40mM), preferably no greater than 30mM, and optimal is 20mM.
5th aspect, with the i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides of manganese oxide minerals of the present invention CP217 may belong to protection scope of the present invention as the microbial bacterial agent of active component.Also, can be according to need in the microbial inoculum Add appropriate auxiliary material.
Mn (II) of the present invention can be MnCl2Or MnSO4
In addition, the it should be appreciated by those skilled in the art that manganese oxide minerals Shinella zoogloeoides of the present invention CP217 or the microbial bacterial agent of manganese oxide minerals comprising the present invention can also be with other heavy metal chelants, Biological decomposers (for example, some mushrooms) is applied in combination, for removing contents of many kinds of heavy metal ion or other pollutants including Mn (II).This Art personnel can be selected according to being actually needed, as long as these are into can play the function that each needs after subassembly Activity.
The present invention also provides a kind of for cultivating the i.e. dynamic glue bacterium sample Shen Salmonella Shinella of manganese oxide minerals Zoogloeoides CP217 (its deposit number is CGMCC NO 13235) culture medium, and trained using the culture medium Foster method, the culture medium contain per in 1L:Peptone 2.0g;Dusty yeast 0.5g;NaCl 0.15M;KCl 0.005M;MgSO4 0.025M;CaCl20.005M;CuSO4·5H2O 10μg;ZnSO4·7H2O 44μg;CoCl2·6H2O 20μg;Na2MoO4· 2H2O 13 μ g, Mn (II) 1-40mM, wherein Mn (II) can be MnCl2Or MnSO4.The culture medium can be fluid nutrient medium (solvent For water), or solid medium.1.5% agar is added wherein in solid medium.The culture medium can be used as Shinella zoogloeoides CP217 culture presevation, pass on and spread cultivation, it is also possible to make screening and culturing medium.
The present invention provides following items:
1st, a kind of i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of manganese oxide minerals, its preservation are compiled Number it is:CGMCC NO 13235 and its application in synthesising biological manganese oxide.
2nd, containing the i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of manganese oxide minerals, (its preservation is compiled Number be CGMCC NO 13235) microbial bacterial agent and its application in synthesising biological manganese oxide.
It is 3rd, a kind of that using the i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of manganese oxide minerals, (it is protected It is CGMCC NO 13235 to hide numbering) method of synthesising biological manganese oxide.
It is 4th, a kind of that using the i.e. dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of manganese oxide minerals, (it is protected It is CGMCC NO 13235 to hide numbering) remove water body or the method for the Mn (II) in solid matrix.
Beneficial effect of the present invention:
(deposit number is CGMCC NO 13235 to the Shinella zoogloeoides CP217 bacterial strains of the present invention.) with 1.0% throwing bacterium amount, can be in Mn (II) concentration 40mM matrix under conditions of 20-30 DEG C, 150rpm, pH 5.0-8.0 Normal growth, and Mn (II) is aoxidized.
The dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217 of the present invention are screened from manganese ore old site soil, energy Existence and synthesising biological manganese oxide under the conditions of the Mn (II) of high concentration.Remove Mn (II) and synthesising biological manganese oxide in water body Have a extensive future.
Brief description of the drawings
The characteristics of Shinella zoogloeoides CP217 are described in detail with reference to accompanying drawing, wherein:
Figure 1A is scannings of the Shinella zoogloeoides CP217 in the culture basal growth stationary phase for not adding Mn (II) Electron microscope.
Figure 1B is that Shinella zoogloeoides CP217 synthesising biological manganese oxide in containing Mn (II) culture medium is swept Retouch electron microscope.
Fig. 2A is growth curves of the Shinella zoogloeoides CP217 in various concentrations Mn (II) matrix.
Fig. 2 B are the song of Shinella zoogloeoides CP217 synthesising biological manganese oxide under various concentrations Mn (II) Line.
Fig. 3 is the curve of Shinella zoogloeoides CP217 synthesising biological manganese oxide under condition of different pH.
Fig. 4 is the curve of Shinella zoogloeoides CP217 synthesising biological manganese oxide under condition of different temperatures.
Sequence table explanation:SEQ ID:1 is Shinella zoogloeoides CP217 16S rDNA sequence tables.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.It is unreceipted specific in embodiment Technology or condition person, carried out according to the technology or condition described by document in the art, or according to product description.It is used Reagent or the unreceipted production firm person of instrument, it is the conventional products that can be commercially available by regular distributor.
Screening and culturing medium composition used below:Contain in per 1.0L:Peptone 2.0g;Dusty yeast 0.5g;NaCl 0.15M; KCl 0.005M;MgSO40.025M;CaCl20.005M;CuSO4·5H2O 10μg;ZnSO4·7H2O 44μg;CoCl2· 6H2O 20μg;Na2MoO4·2H2O 13 μ g, Mn (II) 1-40mM, wherein Mn (II) can be MnCl2Or MnSO4
The Shinella zoogloeoides CP217 of embodiment 1 screening, separation and identification
1st, Shinella zoogloeoides CP217 screening, domestication and separation
Shinella zoogloeoides CP217 are screened from Changping District, Beijing manganese ore old site pedotheque, through sieving One plant of Gram-negative bacteria with synthesising biological manganese oxide performance that choosing, separation and purifying obtain.Comprise the following steps that:
Changping District, Beijing manganese ore old site pedotheque is taken, 1.0g soil is added into 9.0ml sterilized waters vibration 30min After (150rpm, 25 DEG C) stands 10min afterwards, draw 1.0ml supernatants and add the 100ml screening and culturings containing 1.0mM Mn (II) Cultivated in base 10 days (150rpm, 25 DEG C).After shaken cultivation 10 days, draw 1.0ml nutrient solutions and add containing 10mM Mn (II) Culture domestication 10 days in screening and culturing medium.Nutrient solution is diluted to the 10 of stoste with sterilized water-1With 10-2Times.Draw stoste and dilution Each 0.1ml of liquid is applied in the solid screening and culturing medium flat board of 90mm diameters, flat board Mn containing 10mM (II).After culture 7-20 days Brown is presented in picking or the bacterium colony of black is detected with LBB methods.Colourless LBB (LeducoBerbelin Blue) can be made to become blue Bacterial strain is set to positive strain, individually draws flat board and preserves.
Domestication separation is screened more than, obtained Shinella zoogloeoides CP217 are Gram-negative bacterias. In the scanning electron microscopic picture for not reaching growth stationary phase plus in Mn (II) culture medium as shown in Figure 1A, show that the form of bacterium is special Point;As shown in Figure 1B, display biological oxidation manganese is tightly for the scanning electron microscope (SEM) photograph of synthesising biological manganese oxide in containing Mn (II) culture medium It is wrapped in around thalline.
2nd, the structure of the 16S rDNA phylogenetic trees based on Shinella zoogloeoides CP217 structures
16S rDNA identifications comprise the following steps that:
Using the 16s rDNA universal primers 27F (5 '-AGA GTT TGA TCC TGG CTC AG-3 ') reported, 1492R (5 '-AAG GAG GTG ATC CAG CCG CA-3 ') carries out the amplification of target gene.PCR reaction conditions are:98℃ 2min;98℃10s;57℃30s;72℃40s;32 circulations;72℃10min.PCR primer is pure through Axygen glue reclaim kits PEASY-T1 carriers are connected after changing recovery, convert Escherichia coli Trans-phage competent cells, picking positive colony extraction matter Grain, and be sequenced and (completed by Mei Jisangge companies).
CP217 16S rDNA sequences are imported into GenBank and carry out homologous sequence comparison, the results showed that, maximum similar bacterium Strain is Shinella zoogloeoides, similarity 99%.Combining form feature and physio-biochemical characteristics can interpolate that the bacterial strain Belong to Shinella zoogloeoides, be named as dynamic glue bacterium sample Shen Salmonella Shinella zoogloeoides CP217.
The bacterial strain Shinella zoogloeoides CP217 of above-mentioned separation are preserved in China on November 3rd, 2016 Microbiological Culture Collection board of trustee reason person understands common micro-organisms center (abbreviation CGMCC, city of BeiJing, China Chaoyang District North Star West Road 1 No. 3 Institute of Microorganism, Academia Sinica of institute, postcode:100101), deposit number is CGMCC NO 13235.
The properties study of the Shinella zoogloeoides CP217 synthesising biological manganese oxide of embodiment 2
Following Mn (II) can be MnCl2Or MnSO4
Shinella zoogloeoides CP217 growths and synthesising biological manganese oxide under 1 different Mn (II) concentration;
CP217 seed liquors are inoculated into the liquid screening medium containing different Mn (II) concentration by 1/100, Mn (II) Concentration is respectively 1.0,5.0,10.0,20.0,50.0mM, pH value of solution 6.0.Shaken cultivation 10 days (150rpm, 25 DEG C) after inoculation The concentration of bacteria concentration (OD600) and biological oxidation manganese is detected afterwards.Biological oxidation manganese concentration is detected with LBB methods.If Fig. 2A is (in difference The curve of synthesising biological manganese oxide in concentration Mn (II) matrix) shown in, it is seen that CP217 growth is not by the shadow of Mn (II) concentration Ring, tend towards stability.And the biological oxidation manganese synthetic quantity shown in Fig. 2 B (CP217 growth curves under various concentrations Mn (II)) by Mn (II) concentration has a great influence, as the trend for first increasing and being then declined slightly is presented in the rise of Mn (II) concentration.Wherein most Suitable Mn (II) concentration is 20mM.
2 different pH value CP217 synthesising biological manganese oxide.
Liquid screening medium is prepared, Mn (II) concentration is 20mM.Screening and culturing medium is adjusted into pH5.0-8.0.Inoculation With the concentration of LBB methods detection biological oxidation manganese after CP217 seed liquors 1/100 to screening and culturing medium culture 10 days.Such as Fig. 3 (CP217 The curve of synthesising biological manganese oxide under condition of different pH) shown in, CP217 has higher biological oxidation manganese in pH5.0-6.0 Combined coefficient.
CP217 growths and synthesising biological manganese oxide under 3 different temperatures;
CP217 is inoculated into Mn containing 20mM (II) liquid screening medium (pH6.0), is placed into the training of different temperatures Support shaken cultivation in case, 150rpm.With the synthetic quantity of LBB methods detection biological oxidation manganese after 10 days.Such as Fig. 4, (CP217 is in not equality of temperature The curve of synthesising biological manganese oxide under the conditions of degree) shown in, CP217 biological oxidation manganese combined coefficienies at lower or higher temperatures Decline, optimum temperature is 25-30 DEG C.The temperature is the temperature for being relatively easy to reach in application.
To sum up, Shinella zoogloeoides CP217 have Mn (II) oxidation activity in pH 5.0-8.0, and 20-30 DEG C has Mn (II) oxidation activity.Simultaneously synthesising biological manganese oxide can be grown under Mn (II) concentration not higher than 40mM.
Although above the present invention is described in detail with a general description of the specific embodiments, On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
SEQUENCE LISTING
<110>Beijing City Radiation Centre
<120>A kind of manganese oxide minerals and its application
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<160> 1
<170> PatentIn version 3.3
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<211> 1467
<212> DNA
<213>Dynamic glue bacterium sample Shen Salmonella(Shinella zoogloeoides)
<400> 1
ccttagagtt tgatcctggc tcagaacgaa cgctggcggc aggcttaaca catgcaagtc 60
gaacgccccg gtaacgggga gtggcagacg ggtgagtaac gcgtgggaat ctacccaact 120
ctacggaata actcagggaa acttgtgcta ataccgtata cgcccttcgg gggaaagatt 180
tatcggagtt ggatgagccc gcgttggatt agctagttgg tggggtaaag gcctaccaag 240
gcgacgatcc atagctggtc tgagaggatg atcagccaca ttgggactga gacacggccc 300
aaactcctac gggaggcagc agtggggaat attggacaat gggcgcaagc ctgatccagc 360
catgccgcgt gagtgatgaa ggccctaggg ttgtaaagct ctttcaccgg tgaagataat 420
gacggtaacc ggagaagaag ccccggctaa cttcgtgcca gcagccgcgg taatacgaag 480
ggggctagcg ttgttcggaa ttactgggcg taaagcgcac gtaggcgggt atttaagtca 540
ggggtgaaat cccagagctc aactctggaa ctgcctttga tactgggtac ctagagtatg 600
gaagaggtga gtggaattcc gagtgtagag gtgaaattcg tagatattcg gaggaacacc 660
agtggcgaag gcggctcact ggtccattac tgacgctgag gtgcgaaagc gtggggagca 720
aacaggatta gataccctgg tagtccacgc cgtaaacgat gaatgttagc cgtcggcatg 780
catgcatgtc ggtggcgcag ctaacgcatt aaacattccg cctggggagt acggtcgcaa 840
gattaaaact caaaggaatt gacgggggcc cgcacaagcg gtggagcatg tggtttaatt 900
cgaagcaacg cgcagaacct taccagccct tgacatgtcg gtcgcggatt acagagatgt 960
tttccttcag ttaggctgga ccgaacacag gtgctgcatg gctgtcgtca gctcgtgtcg 1020
tgagatgttg ggttaagtcc cgcaacgagc gcaaccctcg cccttagttg ccagcattag 1080
gttgggcact ctaaggggac tgccggtgat aagccgagag gaaggtgggg atgacgtcaa 1140
gtcctcatgg cccttacggg ctgggctaca cacgtgctac aatggtggtg acagtgggca 1200
gcgagacagc gatgtcgagc taatctccaa aagccatctc agttcggatt gcactctgca 1260
actcgagtgc atgaagttgg aatcgctagt aatcgcggat cagcatgccg cggtgaatac 1320
gttcccgggc cttgtacaca ccgcccgtca caccatggga gttggtttta cccgaaggcg 1380
atgcgctaac cgcaaggagg cagtcgacca cggtagggtc agcgactggg gtgaagtcgt 1440
aacaaggtag ccgtagggga acctgcg 1467

Claims (8)

1. dynamic glue bacterium sample Shen Salmonella (Shinella zoogloeoides) CP217, CGMCC NO 13235.
2. containing the microbial bacterial agent that glue bacterium sample Shen Salmonella is moved described in claim 1.
3. microbial bacterial agent described in moving glue bacterium sample Shen Salmonella or claim 2 described in claim 1 is used for synthesising biological manganese oxide Application or application for removing the Mn (II) in water body or solid matrix.
A kind of 4. method of synthesising biological manganese oxide, it is characterised in that including will described in claim 1 move glue bacterium sample Shen Salmonella or Microbial bacterial agent described in nutrient solution or claim 2 containing the bacterium is added in water body or solid matrix, at 20-30 DEG C, pH value To cultivate appropriate time under conditions of 5.0-8.0.
5. a kind of remove water body or the method for the Mn (II) in solid matrix, it is characterised in that including will be moved described in claim 1 Microbial bacterial agent described in glue bacterium sample Shen Salmonella or nutrient solution or claim 2 containing the bacterium is added in water body or solid matrix, At 20-30 DEG C, pH value cultivates appropriate time under conditions of being 5.0-8.0.
6. the method according to claim 4 or 5, it is characterised in that the incubation time is not more than 7 days;
And/or the pH value is 5.0-8.0, preferably pH6.0;
It is optimal to be and/or Mn (II) concentration is not higher than 40mM, preferably no greater than 30mM in the water or in solid matrix 20mM。
7. according to the method described in claim any one of 4-6, it is characterised in that the water body includes but is not limited to Industry Waste Water, sanitary wastewater, underground water or running water;The solid matrix includes but is not limited to soil, deposit.
8. the cultural method of glue bacterium sample Shen Salmonella is moved described in a kind of claim 1, it is characterised in that including using following culture medium Cultivated, contained in the every 1.0L of the culture medium:Peptone 2.0g;Dusty yeast 0.5g;NaCl 0.15M;KCl 0.005M; MgSO40.025M;CaCl20.005M;CuSO4·5H2O 10μg;ZnSO4·7H2O 44μg;CoCl2·6H2O 20μg; Na2MoO4·2H2O 13 μ g, Mn (II) 1-40mM, wherein Mn (II) are MnCl2Or MnSO4
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Cited By (1)

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CN114177887A (en) * 2021-12-02 2022-03-15 中国环境科学研究院 Biochar-manganese composite material wrapping biochar and preparation method and application thereof

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CN101746877A (en) * 2009-07-13 2010-06-23 北京工业大学 Method for oxidizing and removing As in ground water by utilizing manganese to biologically oxidizing intermediate product Mn3+
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Publication number Priority date Publication date Assignee Title
CN114177887A (en) * 2021-12-02 2022-03-15 中国环境科学研究院 Biochar-manganese composite material wrapping biochar and preparation method and application thereof
CN114177887B (en) * 2021-12-02 2023-01-03 中国环境科学研究院 Biochar-manganese composite material wrapping biochar and preparation method and application thereof

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