CN104411370A - Decomposition accelerator for volatile organic halogen compound - Google Patents
Decomposition accelerator for volatile organic halogen compound Download PDFInfo
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- CN104411370A CN104411370A CN201380032349.7A CN201380032349A CN104411370A CN 104411370 A CN104411370 A CN 104411370A CN 201380032349 A CN201380032349 A CN 201380032349A CN 104411370 A CN104411370 A CN 104411370A
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- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/344—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for digestion of mineral oil
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/38—Chemical stimulation of growth or activity by addition of chemical compounds which are not essential growth factors; Stimulation of growth by removal of a chemical compound
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- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
Provided is a decomposition accelerator used in purification (bioremediation) by microorganisms of soil contaminated by a volatile organic halogen compound, wherein said decomposition accelerator can quickly detoxify a volatile organic halogen compound by increasing the decomposition activity of the microorganisms, and in particular, the activity of microorganisms in initial dosing stages. This decomposition accelerator for volatile organic halogen compound is characterized by containing one or more of (A)-(C) below. (A) Citrus fruit or an extract obtained from said fruit (B) Citrus peel or an extract obtained from said peel (C) A formulation containing all of (1)-(3) (1) Glycerin (2) Milk protein and / or yeast extract (3) Vitamin B12
Description
Technical field
The present invention relates to the decomposition accelerating agent of volatility organohalogen compound and decompose promotion method, specifically, relating to and microorganism can be utilized to promote the decomposition accelerating agent that volatility organohalogen compound decomposes and use its decomposition promotion method.
Background technology
The soil in soil, underground water are sometimes by natural or artificial various chemical contaminations.No matter such land pollution is when being used as the arable land being used for grain-production in this soil, still attempt living, commercial exploitation time all can become significant problem.
But different with the diet product of immediate access, the clothes/cosmetics/ornament contacting skin etc., the pollution in soil, particularly soil pollution not too receive publicity, and the past also has landfill chemical substance of digging a hole to carry out the example processed.
The purification of the pollution in such soil becomes significant problem recently, is directed to this, proposes and has carried out various purifying treatment method.
If the purification method in this soil of rough classification, then can be categorized as following four kinds: by high-temperature heating chemical decomposition material or make it be adsorbed in the physical treatment of active carbon etc.; By the chemical treatment that chemical reaction makes chemical substance innoxious; Utilize the microbial cleaning method with the microorganism of chemical decomposition physical capacity; And utilization has the plant purification method of the plant of the ability of absorption or adsorption of chemical species.
Wherein, the method of use microorganism, plant can suppress to get most of the attention recently in the worry to environment, cost, utilize the purification method of microorganism to be also referred to as " biodegradation ", utilize the purification method of plant to be also referred to as " plant degradation ", carry out various research and development, from the bulky aspect of treatable soil, actively carry out biodegradable research and development.
Biodegradation has two kinds of technology.Be the technology having pre-determined the microorganism of the decomposition performance effect for object pollution material in polluted place application, be called as biological reinforced.Another kind is by giving oxygen, nutrient source to the indigenous microorganism of polluted place, and the activity of microorganism is activated, and promotes the technology of catharsis, is called as biostimulation.
In addition, biodegradation has two kinds of methods.One removes contaminated soil, underground water, carries out the method processed, be called as " process of facility type " in other places.Another kind is in the method for this place purification contaminated soil, underground water, is called as " original position purification ".
As the polluter in recent years becoming significant problem, the organohalogen compound that to have with organochlorine compounds such as tetrachloro-ethylene, trichloro-ethylene, dichloroethylene, dioxin, polychlorinated biphenyls be representative.Wherein, about volatility organohalogen compounds such as tetrachloro-ethylene, trichloro-ethylene, dichloroethylene, worry the impact by breathing human body, therefore common have the situation needing to process as early as possible.
This volatility organohalogen compound easily soaks into soil, arrives underground water Veins, easily expands and pollutes extremely in a big way.Although the edaphon of decomposing such volatility organohalogen compound also exists, but in general soil is more more close to surface organic matter, edaphon also exists in a large number, and along with all reducing from top layer to deep organic matter and edaphon, if be deep into more than 1m, the activity of microorganism is reduced to less than 1/100 of top layer.Accordingly, once be there is long-time low concentration by volatility organohalogen compound contaminated land and contaminated problem in a big way.
Such low concentration and in a big way the purification in contaminated soil be effective means with biodegradation, so propose the various schemes using the pollution of purifying volatile organohalogen compound as object.
Such as propose following scheme: utilize the biostimulation (for example, see patent document 1) comprising the composition of the ester of the polyfunctional alcohol such as PLA and glycerine, xylitol, D-sorbite, pentaerythrite; Utilize the biostimulation (for example, see patent document 2) comprising the composition of yeast, aliphatic acid, carbohydrate etc.; Utilize the biostimulation (for example, see patent document 3) of the condensation reaction products of amino acid and hydroxycarboxylic acid.It should be noted that, in non-patent literature 1, record the method for soil and/or the groundwater contacts that various decomposition accelerating agent and microorganism are existed.
On the other hand, as the microorganism that uses by the purification of volatility organohalogen compound contaminated land there will be a known Anaerobic Bacteria, particularly dehalogenation and intend Coccus bacterium.If the non-existent state of this microorganism, then till volatility organohalogen compound can not decompose to final ethene, but decompose the dichloroethylene that may be parked in as intermediate material, therefore may cause and cannot purify completely.But, also there will be a known: even such as dehalogenation is intended, Coccus bacterium is also usual determines decomposable compound according to its kind, needs multiple dehalogenation intend coccus participation (see non-patent literature 2) from tetrachloro-ethylene to the decomposition of ethene.Therefore, the various volatility organohalogen compound decomposition rates of dehalogenation plan Coccus bacterium might not be fast, in addition, even if there is dehalogenation to intend the decomposition that Coccus bacterium also not necessarily participates in volatility organohalogen compound.
Therefore, propose there is following scheme: use multiple dehalogenation to intend the hybrid bacterial strain of Coccus bacterium biological reinforced (for example, see non-patent literature 3); Dehalogenation is used to intend Coccus bacterium and streptococcus biological reinforced (for example, see patent document 4) as the flora (consortia) of main thalline.But, use the method for this hybrid bacterial strain also to there is the problem causing purification speed to postpone by the pollution condition of soil, pH and then the content of organic matter.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Application Publication 2000-511969 publication
Patent document 2: Japanese Unexamined Patent Publication 2005-185870 publication
Patent document 3: Japanese Unexamined Patent Publication 2010-104962 publication
Patent document 4: Japanese Unexamined Patent Publication 2011-244769 publication
Non-patent literature
Non-patent literature 1: Co., Ltd.'s census of manufacturing meeting " chemical devices " in July, 2007 number, mountain rugged abundant " the decomposing, purifying technology-of soil/ground water cleaning technology-VOC " (Co., Ltd. work industry Tone Check meeting " chemical devices " in July, 2007 number, mountain rugged abundant " native Reel ground water cleaning skill Intraoperative-VOC decomposing, purifying skill Intraoperative-")
Non patent literature 2: Qi Yuansheng he "vinyl chloride as the original object position in biodegradation dehalogenation quasi behavior analysis" Staphylococcus bacteria on groundwater / soil pollution and its preventing countermeasure research rally speeches (2008) (Qi Sheng he as as the original "Danish" stories, or class or control like the original position and hyperplastic clima Ohio or media data, so major systems, and at Dehalococcoides in in bacteria of the genus of behavior analytic "groundwater and soil pollution and method for preventing countermeasures in studies of Japanese research rally in speech collection (2008))
Non-patent literature 3: vow that wood is cultivated one's moral character " present situation and the prospect from now on of land remediation technology " " seeking the harmful chemical-main idea collection 10 pages in the safety-agricultural aquatic ecosystem system of food and environment " (2007) (vowing that wood is cultivated one's moral character " soil is repaiied the modern Hou of Complex skill Intraoperative Now shape と and looked forward to " " eating the safe The in と Ring border asks め て-Farming woods aquatic ecosystem system To お け Ru to be harmful to chemicals Quality-main idea collection 10 ペ ー ジ " (2007))
Summary of the invention
the problem that invention will solve
But, about the method described in patent document 1, patent document 3, the activity of the microorganism of administration starting stage is low, therefore, for contaminated soil, particularly underground water particularly in a large number containing volatility organohalogen compound, there is the problem of low, the innoxious length of required time of purified treatment speed.In addition, about the method described in patent document 2, although there is the effect of the decomposition reaction promoting volatility organohalogen compound, the activation of microorganism is still insufficient, still there is the problem of innoxious length of required time.On the other hand, as non-patent literature 3, the disclosed method using hybrid bacterial strain of patent document 4, also there is the problem causing purification speed to postpone because of the pollution condition of soil, pH and then the content of organic matter.
Therefore, the object of the present invention is to provide decomposition accelerating agent, it is for being utilized the decomposition accelerating agent used in the purification (biodegradation) of microorganism by volatility organohalogen compound contaminated land, particularly by improving the activity of the microorganism of administration starting stage, volatility organohalogen compound can be made innoxious rapidly.
In addition, the object of the present invention is to provide and utilize microorganism to promote the method that volatility organohalogen compound decomposes, when it is for being utilized microorganism to carry out purifying (biodegradation) by volatility organohalogen compound contaminated land, particularly by improving the activity of the microorganism of administration starting stage, the method that volatility organohalogen compound is innoxious rapidly can be made.
for the scheme of dealing with problems
The present inventor etc. have carried out various research to reach above-mentioned purpose, found that, when using in following (A) ~ (C) a kind or two or more decomposition accelerating agent as volatility organohalogen compound, effectively can promote that volatility organohalogen compound utilizes the decomposition of microorganism, thus complete the present invention.
That is, the feature of the decomposition accelerating agent of volatility organohalogen compound of the present invention is, its contain in following (A) ~ (C) a kind or two or more.
(A) fruit of citrus or the extract that obtained by this fruit
(B) pericarp of citrus or the extract that obtained by this pericarp
(C) containing the blend that following (1) ~ (3) are whole
(1) glycerine
(2) lactoprotein and/or yeast extract
(3) vitamin B12
In addition, preferably, when decomposition accelerating agent of the present invention contains at least a kind in (A) and (B), aforementioned extract is the extract obtained using water as solvent.
Preferably, when decomposition accelerating agent of the present invention contains (C), relative to glycerine 1 mass parts of aforementioned (1), containing lactoprotein and/or the yeast extract of counting aforementioned (2) of 0.1 ~ 3 mass parts with solid constituent.
In addition, preferably, when decomposition accelerating agent of the present invention contains (C), relative to glycerine 1 mass parts of aforementioned (1), the vitamin B12 of aforementioned (3) containing 0.00001 ~ 0.001 mass parts.
The feature of decomposition accelerating agent composition of the present invention is, it contains decomposition accelerating agent as active ingredient.
Of the present invention utilize microorganism to promote the feature of the method that volatility organohalogen compound decomposes is, make above-mentioned arbitrary decomposition accelerating agent or above-mentioned decomposition accelerating agent composition and the soil and/or the groundwater contacts that comprise volatility organohalogen compound.
In the method for the invention, preferred aforementioned volatility organohalogen compound is organochlorine based compound.
In addition, in the method for the invention, preferably, aforementioned organochlorine compound is for being selected from by carbon tetrachloride, chloroform, carrene, monochloro methane, 1,2-dichloroethanes, vinylidene chloride, cis-1,2-dichloroethene, anti-form-1,2-dichloroethylene, 1,3-dichloropropylene, tetrachloro-ethylene, 1,1,1-trichloroethanes, 1, at least a kind in the group of 1,2-trichloroethanes, trichloro-ethylene and vinyl chloride composition.
In addition, in the method for the invention, preferably, at least a kind in the group that aforementioned micro organism intends Coccus (Dehalococcoides) bacterium for being selected from by fusobacterium (Clostridium) bacterium, dehalogenate Bacillus (Dehalobacter) bacterium, dehalogenation, dehalogenation Spirillum (Dehalospirilum) bacterium, Desulfobacter (Desulfobacterium) bacterium, Desulfomonas (Desulfomonas) bacterium and desulfurization Mycotoruloides (Desulfomonile) bacterium form.
the effect of invention
Decomposition accelerating agent of the present invention easily processes, by using in the purification (biodegradation) being utilized microorganism by volatility organohalogen compound contaminated land, contaminated soil, underground water can be made innoxious rapidly, and at a low price and free of a burden to environment.
In addition, method low cost of the present invention is also free of a burden to environment, can promote by the purification of volatility organohalogen compound contaminated soil, groundwater use microorganism.
Accompanying drawing explanation
Fig. 1 is the curve map of passing of c-DCE, the VC represented in embodiment 1, ethene amount.
Fig. 2 is the curve map of passing of c-DCE, the VC represented in embodiment 2, ethene amount.
Fig. 3 is the curve map of passing of c-DCE, the VC represented in comparative example 1, ethene amount.
Fig. 4 is the curve map of passing of c-DCE, the VC represented in comparative example 2, ethene amount.
Fig. 5 is the curve map of passing of the trichloro-ethylene represented in embodiment 7, c-DCE, VC, ethene amount.
Fig. 6 is the curve map of passing of the trichloro-ethylene represented in comparative example 3, c-DCE, VC, ethene amount.
Fig. 7 is the curve map of passing of amount of the trichloro-ethylene represented in embodiment 15, dichloroethylene, vinyl chloride, ethene.
Detailed description of the invention
Below, the decomposition accelerating agent of volatility organohalogen compound of the present invention is described in detail.It should be noted that, in this manual, the decomposition of volatility organohalogen compound refers to the dehalogenate of volatility organohalogen compound.
The feature of the decomposition accelerating agent of volatility organohalogen compound of the present invention is, its contain in following (A) ~ (C) a kind or two or more.
(A) fruit of citrus or the extract that obtained by this fruit
(B) pericarp of citrus or the extract that obtained by this pericarp
(C) containing the blend that following (1) ~ (3) are whole
(1) glycerine
(2) lactoprotein and/or yeast extract
(3) vitamin B12
First, above-mentioned (A) composition and (B) composition are described.
For the kind of the citrus of above-mentioned (A) composition and (B) composition, not special restriction, as long as be the plant belonging to Rutaceae Aurantioideae, particularly contained in Rutaceae Aurantioideae Citrus or Fortunella plant, preferably by the plant using this Citrus, Fortunella hybridization etc. to produce.As the concrete example of citrus, such as, can enumerate: late logical sequence West Asia orange, navel orange, blood orange, grape fruit, lemon, shaddock, bitter orange, citrus unshiu Marcovitch, eight the first day of the lunar month, Gan Xia, pomelo, golden mandarin orange, tangerine so these hybridization etc. produce she give mandarin orange, see clearly, do not know fire etc. the tangelos etc. such as oranges and tangerines, Seminole, bright Buddhist nun tangelo.Wherein, from easily obtaining and the aspect that can obtain at a low price in a large number, preferably use in late logical sequence West Asia orange, grape fruit, lemon, citrus unshiu Marcovitch more than one.
For above-mentioned (A) composition and (B) composition, can be the whole fruit of above-mentioned citrus, also can be a part for fruit, but from decomposing the high aspect of facilitation effect, preferred pericarp.
For the form of above-mentioned (A) composition and (B) composition, have no particular limits, such as, can enumerate: the form that fruit, pericarp, pulp directly use; The form of fruit, pericarp, pulp drying; Fruit, pericarp, pulp are scattered in the form of water through pulverizing; Fruit, pericarp, pulp are through the form of powdered; Fruit juice etc.In addition, also can be the extract extracted from fruit, particularly pericarp with the water such as warm water, hot water; With the extract of the non-polar solvent extract such as ethanol, acetone, ethyl acetate polar solvent, hexane.
Wherein, when the extract that pericarp extracts is applied to soil, there is prompt effect with the water such as warm water, hot water, in addition from the viewpoint obtaining high effect be preferred.It should be noted that, during extraction, the temperature of water is preferably 30 ~ 100 DEG C, is more preferably 60 ~ 95 DEG C, more preferably 60 ~ 80 DEG C.
As the extraction and isolation device that said extracted uses, as long as be the device of the extract that effectively can obtain the decomposition accelerating agent forming volatility organohalogen compound of the present invention, such as, can enumerate: continuous centrifugal device, membrane separation device, means of supercritical extraction device etc.
It should be noted that, pericarp a large amount of by-product when manufacturing time processing product (fruit juice, the can etc.) of citrus fruits of citrus, there is no useful purposes at present and major part is dropped, the decomposition accelerating agent of volatility organohalogen compound of the present invention it can be used as raw material, the product of the decomposition accelerating agent cheapness than volatility organohalogen compound known at present can not only be provided, and also be significant from the aspect that effectively utilizes of resource.
And then, for the said extracted thing of a form of above-mentioned (A) composition and (B) composition, can be the extract extracted the residue after extracting the compositions such as pectin, fragrance component, pigment, hesperidin from fruit, also can containing the composition beyond these.
It should be noted that, the fruit of citrus is eaten since ancient times, it can be used as the decomposition accelerating agent of the volatility organohalogen compound of the present invention of raw material high and also easily process the aspect that heat is also more stable from security.
As above-mentioned (A) composition and (B) composition, in the fruit of citrus, particularly its pericarp plays high de-agglomeration facilitation effect, and in addition, the effect of being got the extract of acquisition by the water extraction of warm water, hot water etc. is high.Therefore, though detailed reason is unclear, as a possibility, think that composition contained in the citrus fruits of the effect playing decomposition accelerating agent of the present invention is the mixture of water-soluble saccharides, salt, organic acid.
Then, above-mentioned (C) composition is described.
Above-mentioned (C) composition is containing the whole blend in following (1) ~ (3).
(1) glycerine
(2) lactoprotein and/or yeast extract
(3) vitamin B12
The carbon source that the glycerine used in the blend of above-mentioned (C) composition is microorganism, and become the supply source of the hydrogen of the chlorine atom for replacing organochlorine based compound, i.e. hydrogen donor, glycerine itself can be used, also for being combined with the form of the glyceride of 1 ~ 3 aliphatic acid, preferably glycerine itself can be used.When using commercially available glycerine, be not limited to purity be the glycerine of 100%, more than 99% (such as, reagent is superfine), also can use the glycerine of Japanese Pharmacopoeia (purity 80 ~ 90%), purification of glycerol D, food additives glycerine, concentrated glycerin used for cosmetic (being Lion Corporation. to manufacture) etc.
In the blend of above-mentioned (C) composition, use lactoprotein and/or yeast extract as the nitrogenous source of microorganism.
As above-mentioned lactoprotein, lactalbumin can be only, be only casein, any person combinationally used in casein and lactalbumin, but more preferably combinationally use lactalbumin and casein.
In addition, above-mentioned lactoprotein is preferably water-soluble.When using commercially available lactoprotein, as long as be the goods containing lactoprotein with high concentration, and food is used, the harmless lactoprotein (or the lactoprotein of growth of microorganism can not be hindered significantly) such as used for cosmetic, such as can enumerate: casein-sodium, potassium caseinate, whey powder, WPC (whey protein concentrate), WPI (lactalbumin isolate), total milk protein (TMP), protein compression whey powder, full milk powder, skimmed milk power, Reduced lactose whey, Reduced lactose whey powder, buttermilk powder, sweetened powdered milk, modified milk powder, lactoprotein concentrate (MPC) etc.In the present invention, the low and aspect that storage stability is high from lipid content, is preferably total milk protein (TMP) and/or skimmed milk power, is more preferably skimmed milk power.
Above-mentioned yeast extract refers to by carrying out the process such as self-dissolving, enzyme, hot water, physics broken, sour decomposition, caustic digestion, freezing fusion method to the culture of yeast thus the extract extracted.To the not special restriction of the kind of the yeast used in the manufacture of yeast extract, Saccharomyces cerevisiae, brewer's yeast, wine yeast, torula etc. can be used without particular limitation.Wherein, the yeast belonging to saccharomyces (Saccharomyces) is preferably used.Yeast extract can be any person in pasty state, Powdered, graininess.
In above-mentioned lactoprotein of the present invention and yeast extract, can only use above-mentioned lactoprotein, also only can use yeast extract in addition, but preferably only use lactoprotein, further preferred compositions to use lactoprotein and yeast extract.
Wherein, for mixing ratio when combinationally using, relative to lactoprotein 1 mass parts, make yeast extract be preferably 0.1 ~ 2 mass parts with solid component meter, be more preferably 0.3 ~ 1 mass parts.
In the blend of above-mentioned (C) composition, for the content ratio of the glycerine of above-mentioned (1), the lactoprotein of (2) and/or yeast extract, relative to glycerine 1 mass parts of above-mentioned (1), the lactoprotein of above-mentioned (2) and/or yeast extract is made to be preferably 0.1 ~ 3 mass parts with solid component meter, to be more preferably 0.1 ~ 1 mass parts.
In the blend of above-mentioned (C) composition, use vitamin B12.
Vitamin B12 is the general name of the vitamin containing cobalt, is the one of water soluble vitamin, has hydroxocobalamine, adenosylcobalamin, methyl cobalamin, cyanocobalamin, sulphitocobalamine etc., can use its any person in the present invention.
Its purifying product can be used in the present invention, in addition, also can use a large amount of food containing vitamin B12.Such as, vitamin B12 is mostly containing in the liver of sea sedge, shellfish, animal food.
In the blend of above-mentioned (C) composition, for the content ratio of the glycerine of above-mentioned (1), the vitamin B12 of (3), relative to glycerine 1 mass parts of above-mentioned (1), the vitamin B12 of above-mentioned (3) is made to be preferably 0.00001 ~ 0.001 mass parts, to be more preferably 0.00002 ~ 0.0001 mass parts.
The decomposition accelerating agent of volatility organohalogen compound of the present invention can containing other compositions except above-mentioned (A) composition, (B) composition, (C) composition.
As other compositions above-mentioned, such as, can with the potassium compound such as glucose, fructose, ammonium sulfate, urea, ammonium salt, sulphur compound, phosphorus compound, potassium chloride of nutrient source becoming microorganism, the magnesium compound such as magnesium chloride, magnesium sulfate, yeast extract or peptone etc. use together.In addition, relative to decomposition accelerating agent of the present invention, the decomposition accelerating agent composition of the above-mentioned additive that with the addition of appropriate amount can also be formed.When forming decomposition accelerating agent composition, to the not special restriction of the compounding amount of each additive, such as, when using powder yeast extract, fructose, relative to solid constituent 100 mass parts of the extract of fruit, be preferably 1 ~ 200 mass parts with solid component meter separately, be more preferably 10 ~ 100 mass parts.
Wherein, during as the present invention's use (C) composition, as other compositions above-mentioned, preferably do not contain the composition of the nutritional labeling that can become microorganism, such as: magnesium compound or the peptones etc. such as the potassium compounds such as glucose, fructose, ammonium sulfate, urea, ammonium salt, sulphur compound, phosphorus compound, potassium chloride, magnesium chloride, magnesium sulfate.When particularly there is sulfatereducting bacteria in soil, underground water, compete at coexist lower and this sulfatereducting bacteria of sulfate ion, therefore become the decomposition cannot carrying out volatility organohalogen compound, therefore preferably do not comprise the sulfate such as ammonium sulfate, magnesium sulfate.
To the not special restriction of the form of the decomposition accelerating agent of volatility organohalogen compound of the present invention, the various forms such as solid (comprising Powdered, graininess), liquid (comprising pasty state) can be adopted.In addition, also can use under the state utilizing water equal solvent to dilute.
Decomposition accelerating agent of the present invention by with by volatility organohalogen compound contaminated soil, underground water, other sample contacts, promote that this volatility organohalogen compound utilizes the decomposition of microorganism.The volatility organohalogen compound becoming object of the present invention is preferably organochlorine based compound, such as can enumerate: carbon tetrachloride, chloroform, carrene, monochloro methane, 1,2-dichloroethanes, vinylidene chloride, cis-1,2-dichloroethene, anti-form-1,2-dichloroethylene, 1,3-dichloropropylene, tetrachloro-ethylene, 1,1,1-trichloroethanes, 1,1,2-trichloroethanes, trichloro-ethylene, vinyl chloride etc.
Wherein, decomposition accelerating agent of the present invention can promote the decomposition of the vinyl chloride classes such as tetrachloro-ethylene, trichloro-ethylene, dichloroethylene class, vinyl chloride aptly.
Such as, tetrachloro-ethylene is broken down into trichloro-ethylene, dichloroethylene, a vinyl chloride (vinyl chloride), ethene successively by microorganism.
Decomposition accelerating agent of the present invention is the decomposition promoting that volatility organohalogen compound utilizes microorganism, the microorganism becoming and originally exist in the purification soil of object, underground water can be utilized, also can use the microorganism useful to the decomposition of volatility organohalogen compound simultaneously.In addition, also can use the composition comprising mentioned microorganism simultaneously.That is, decomposition accelerating agent of the present invention can be made when becoming and fully comprising the microorganism of decomposing volatile organohalogen compound in the purification soil of object, underground water, decomposition accelerating agent composition directly applies to object soil.On the other hand, when the microbial biomass in soil is less, or when wishing to accelerate to decompose, can together use decomposition accelerating agent of the present invention, decomposition accelerating agent composition with pre-prepd microorganism, the composition that comprises microorganism.
As the microorganism useful to the decomposition of volatility organohalogen compound, be preferably anerobe, such as, can enumerate: fusobacterium, dehalogenate Bacillus, dehalogenation intend the microorganisms such as Coccus, dehalogenation Spirillum, Desulfobacter, Desulfomonas, desulfurization Mycotoruloides.
When using decomposition accelerating agent of the present invention, preferably measure the anerobe comprised in the sample of volatility organohalogen compound in advance, such as, dehalogenation intends the amount of Coccus bacterium.What dehalogenation intended Coccus bacterium quantitatively can utilize the known methods such as real-time PCR methodology (such as, see non-patent literature 1).
Do not limit especially for making the method for decomposition accelerating agent of the present invention and soil and/or groundwater contacts, can be remove contaminated soil, underground water, carry out in other place " process of facility type " that process, also can at the purification of this place contaminated soil, underground water " original position purification ", but under the condition of anaerobism, play this effect from the microorganism of decomposing volatile organohalogen compound to greatest extent, be preferably original position purification.
When facility type purifies, the method making decomposition accelerating agent of the present invention with the soil and/or groundwater contacts that there is microorganism not being limited especially, such as, can enumerate: piling up the contaminated soil through excavating, the method directly injected wherein; With the method for contaminated soil mix and blend; Add water in contaminated soil and carry out the method etc. of adding with the form of the shape ~ liquid state that flows.
When purifying in situ, the method making decomposition accelerating agent of the present invention with the soil and/or groundwater contacts that there is microorganism is not limited especially, such as, can be: the method being directly embedded in soil; Use Injection Well is injected into the direct injection in underground water or soil; Use the method for the permeability reaction purification wall utilizing the flowing of underground water, but be preferably direct injection.
It should be noted that, as long as the quantity delivered of decomposition accelerating agent of the present invention is the degree that can obtain sufficient clean-up effect, decided by the scope of the Polluted area of pretesting determination in advance, the degree of pollution, the kind etc. of polluter.
Embodiment
The decomposition experiment 1> of < vinyl chloride class
(manufacture 1 of decomposition accelerating agent)
The manufacture > of < citrus extract
(Production Example 1)
After abundant washing citrus unshiu Marcovitch, peeling, after utilizing disc flour mill to pulverize pericarp (dry weight 100g), stirs extraction 1 hour with the warm water 2000ml of 60 DEG C.Filtered, filtrate utilizes vacuum drier to carry out drying after utilizing rotary evaporator concentrated, thus obtains the pericarp warm water extract (about 10g) of citrus unshiu Marcovitch.Using the pericarp warm water extract of acquisition directly as decomposition accelerating agent A of the present invention.
(Production Example 2)
Relative to pericarp warm water extract 100 mass parts obtained in Production Example 1, add powder yeast extract 50 mass parts and fructose 50 mass parts and mix in heterogeneity, it can be used as decomposition accelerating agent B of the present invention.
(Production Example 3)
Use 98 DEG C of hot water to replace extracting the 60 DEG C of warm water used, in addition, obtain decomposition accelerating agent C of the present invention in the same manner as Production Example 1.
(Production Example 4)
Use late logical sequence West Asia orange to replace citrus unshiu Marcovitch, in addition, obtain decomposition accelerating agent D of the present invention in the same manner as Production Example 1.
(Production Example 5)
Use grape fruit to replace citrus unshiu Marcovitch, in addition, obtain decomposition accelerating agent E of the present invention in the same manner as Production Example 1.
(Production Example 6)
Use lemon to replace citrus unshiu Marcovitch, in addition, obtain decomposition accelerating agent F of the present invention in the same manner as Production Example 1.
(evaluation method 1 of decomposition accelerating agent)
The making > of < bacterium liquid
(about decomposition accelerating agent A ~ F)
The culture medium 50mL adding yeast extract in the mode of 0.1g/L in mineral matter basal medium as follows is taken to 100mL volumetric glass bottle, after nitrogen displacement, after utilizing autoclave to carry out sterilization treatment, add from the underground water 25mL that takes by vinyl chloride class contaminated soil, after nitrogen displacement, enclose hydrogen 2.5mL and cis-1,2-dichloroethene 0.58 μ L (being equivalent to 10mg/L), dark place quiescent culture at 20 DEG C.Vinyl chloride class in results of regular determination headroom, takes 1mL in the moment not detecting vinyl chloride class, in the mineral matter basal medium 75mL that the autoclaving continuing to be seeded to interpolation yeast extract 0.1g/L is crossed.Using carrying out this material again cultivating 6 times as " bacterium liquid ", for the decomposition experiment of following vinyl chloride class.
The manufacture > of < mineral matter basal medium (pH7.0 ~ 7.5)
Following salt storing solution 10ml, following trace element solution A 1ml, following trace element solution B1ml, resazurin sodium solution (0.5%w/v) 50 μ l, sodium acetate 0.1g, L-cysteine hydrochloride monohydrate 0.3g, sodium acid carbonate 2.52g, vulcanized sodium nonahydrate 0.048g are filled up to 1000ml, it can be used as mineral matter basal medium.
The manufacture > of < salt storing solution
Following compositions is filled up to 1000ml, as salt storing solution by water-soluble solution.
100g NaCl、50g MgCl
2·6H
2O、20g KH
2PO
4、30g NH
4Cl、30g KCl、1.5gCaCl
2·2H
2O
The manufacture > of < trace element solution A
Following compositions is filled up to 1000ml, as trace element solution A by water-soluble solution.
10mL HCl (25% solution, w/w), 1.5g FeCl
24H
2o, 0.19g CoCl
26H
2o, 0.1gMnCl
24H
2o, 70mg ZnCl
2, 6mg H
3bO
3, 36mg Na
2moO
42H
2o, 24mg NiCl
26H
2o, 2mg CuCl
22H
2o
The manufacture > of < trace element solution B
Following compositions is filled up to 1000ml, as trace element solution B by water-soluble solution.
6mg Na
2SeO
3·5H
2O、8mg Na
2WO
4·2H
2O、0.5g NaOH
The decomposition experiment 1> of < vinyl chloride class
(embodiment 1)
Assuming that the underground water polluted by vinyl chloride class, carry out decomposition run by following method.
Above-mentioned mineral matter basal medium 75ml is taken in the bottle of glass 100ml capacity, adds above-mentioned decomposition accelerating agent A in the mode of 0.1g/L, after nitrogen displacement, carry out sterilization treatment with autoclave.After cooling, add above-mentioned bacterium liquid 1.5ml, after nitrogen displacement, enclose cis-1,2-dichloroethene (c-DCE) in the mode of 10 μ g/ml.
At 20 DEG C, this bottle is carried out quiescent culture.After 0 day, 3 days, 10 days, 18 days, 24 days, 36 days, 45 days, 49 days, 59 days, 66 days, 75 days, 84 days, 87 days, by cis-1,2-dichloroethene (c-DCE) content in the headroom of gas chromatography determination bottle, vinyl chloride (VC) content, ethylene contents.
About experimental result, first, 0th day ~ the 87th day shown in Figure 1 cis-1,2-dichloroethene (c-DCE) content, vinyl chloride (VC) content, ethylene contents growth and decline.
In addition, consider that the activation of microorganism initially causes, therefore the reduction of every 1 day of c-DCE content of near 18th day is shown in table 1 as initial decomposition speed.
(embodiment 2)
Add decomposition accelerating agent B in the mode of 0.2g/L and replace decomposition accelerating agent A 0.1g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 1, result is recorded in Fig. 2 and table 1.
(comparative example 1)
Do not add decomposition accelerating agent A 0.1g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 1, result is recorded in Fig. 3 and table 1.
(comparative example 2)
Do not add decomposition accelerating agent B 0.2g/L, and add yeast extract 0.05g/L and fructose 0.05g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 2, result is recorded in Fig. 4 and table 1.
(embodiment 3)
Add decomposition accelerating agent C in the mode of 0.1g/L and replace decomposition accelerating agent A 0.1g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 1.Wherein, sampling be set to the 0th day, the 3rd day, the 10th day, the 18th day, till the 18th day, the reduction being calculated to every 1 day of the content of the c-DCE of the 18th day is similarly to Example 1 shown in table 1 as initial decomposition speed.
(embodiment 4)
Add decomposition accelerating agent D in the mode of 0.1g/L and replace decomposition accelerating agent A 0.1g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 1.In addition, during sampling is set to similarly to Example 3, only calculate initial decomposition speed, result is recorded in table 1.
(embodiment 5)
Add decomposition accelerating agent E in the mode of 0.1g/L and replace decomposition accelerating agent A 0.1g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 1.In addition, during sampling is set to similarly to Example 3, only calculate initial decomposition speed, result is recorded in table 1.
(embodiment 6)
Add decomposition accelerating agent F in the mode of 0.1g/L and replace decomposition accelerating agent A 0.1g/L, in addition, carry out the decomposition experiment of vinyl chloride class similarly to Example 1.In addition, during sampling is set to similarly to Example 3, only calculate initial decomposition speed, result is recorded in table 1.
[table 1]
※ unit=(μ g/l/ days)
From comparative example 1 result (Fig. 3) obviously, even if when being only minimal medium by the 87th day still residual c-DCE, VC also have rising trend, do not find the situation producing ethene, the decomposition of vinyl chloride class is not almost carried out.
On the other hand, from embodiment 1 (Fig. 1), embodiment 2 result (Fig. 2) obviously, for the sample that with the addition of decomposition accelerating agent of the present invention, be almost decomposed at the 50th day c-DCE, be all almost decomposed completely at the 87th day c-DCE, VC.
It should be noted that, comparing embodiment 2 (Fig. 2) and comparative example 2 (Fig. 4) obviously known, relative to the sample using current nutritional agents and yeast extract and fructose, decomposition accelerating agent of the present invention is added by adding in this nutritional labeling, c-DCE is more promptly decomposed, particularly significantly rises at the decomposition rate of 18th ~ 50 days.The date of same display VC Cmax becomes the 24th day (embodiment 2, Fig. 2) from the 59th day (comparative example 2, Fig. 4), therefore can confirm: adding decomposition accelerating agent of the present invention by adding in current nutritional agents, initial decomposition rate can be increased substantially.
In addition, from table 1 obviously, by adding decomposition accelerating agent of the present invention, initial decomposition rate significantly rises.
It should be noted that, although use the sample of current nutritional agents and yeast extract and fructose also to have certain decomposition rate to improve effect, but comparing embodiment 1,3 ~ 6 and comparative example 2 obviously known, when using decomposition accelerating agent of the present invention, decompose facilitation effect high.And then from the result of embodiment 2, by additional interpolation decomposition accelerating agent of the present invention, initial decomposition rate significantly rises.
(embodiment 7 and comparative example 3)
Assuming that by vinyl chloride class contaminated land, carry out decomposition run by following method.
In 1L capacity screw top jar, put into from the soil 700g taked by trichloro-ethylene contaminated land, the underground water 300g that takes from identical place, after adding above-mentioned bacterium liquid 5mL, add after decomposition accelerating agent A 0.2g and yeast extract 0.2g is dissolved in 50mL distilled water, after nitrogen displacement, in the dark carry out quiescent culture under room temperature.Regularly by the concentration of vinyl chloride class (trichloro-ethylene, c-DCE, VC) in gas chromatography determination headroom and the concentration of ethene.Vinyl chloride class headed by the trichloro-ethylene comprised in Polluted Soil and underground water all became environmental benchmark value (trichloro-ethylene=0.03mg/l, dichloroethylene=0.04mg/l, VC=0.002mg/l) below afterwards at the 120th day.Result is shown in Fig. 5.Wherein, when interpolation fructose 0.2g replacement decomposition accelerating agent A (comparative example 3), even if still remain with amount more than groundwater environment a reference value through 150 days VC, soil can not be purified.Result is shown in Fig. 6.
The decomposition experiment 2> of < vinyl chloride class
(manufacture 2 of decomposition accelerating agent)
(Production Example 7 ~ 16)
According to record the mixing glycerine as (1) composition, the skimmed milk power as (2) composition and/or the yeast extract powder of table 2, the Vitamin B12 preparation as (3) composition, obtain decomposition accelerating agent G ~ P.It should be noted that, in the decomposition accelerating agent of acquisition, G ~ N and P is pasty state, O is Powdered.
It should be noted that, about (1): the content ratio of (2) and (1): the content ratio of (3) is also recorded in table 2.
About the decomposition accelerating agent G ~ P obtained, evaluate according to the evaluation method of following decomposition accelerating agent, result is recorded in table 2.
(evaluation method 2 of decomposition accelerating agent)
The making > of < bacterium liquid
The culture medium 50mL adding yeast extract in the mode of 0.1g/L in above-mentioned mineral matter basal medium is taken to 100mL volumetric glass bottle, after nitrogen displacement, after utilizing autoclave to carry out sterilization treatment, add the underground water 25mL from being taked by vinyl chloride class contaminated soil, after nitrogen displacement, enclose hydrogen 2.5mL and cis-1,2-dichloroethene 0.58 μ L (being equivalent to 10mg/L), dark place quiescent culture at 20 DEG C.Vinyl chloride class in results of regular determination headroom, takes 1mL in the moment not detecting vinyl chloride class, in the mineral matter basal medium 75mL that the autoclaving continuing to be seeded to interpolation yeast extract 0.1g/L is crossed.This material again cultivating 6 times (being for the 6th time only wherein without adding yeast extract) will be carried out as " bacterium liquid ", for the decomposition experiment of following vinyl chloride class.
The decomposition experiment 2> of < vinyl chloride class
(embodiment 8 ~ 14, comparative example 4 ~ 6)
Assuming that the underground water polluted by vinyl chloride class, carry out decomposition run by following method.
Above-mentioned mineral matter basal medium 75ml is taken in the bottle of glass 100ml capacity, adds above-mentioned decomposition accelerating agent G ~ P in the mode of respective 0.3g/L, after nitrogen displacement, carry out sterilization treatment with autoclave.After cooling, add above-mentioned bacterium liquid 1.5ml, after nitrogen displacement, enclose cis-1,2-dichloroethene (c-DCE) in the mode of 10 μ g/ml.
At 20 DEG C, this bottle is carried out quiescent culture.Regularly by c-DCE content, VC content, the ethylene contents in the headroom of gas chromatography determination bottle.About experimental result, using c-DCE content and VC content until become below groundwater environment a reference value, i.e. c-DCE become below 0.04mg/L and the VC number of days that becomes the moment of below 0.002mg/L as " number of days to required for decomposing ", be recorded in table 2.
It should be noted that, similarly test as comparative example 7 without the situation of adding decomposition accelerating agent, result is recorded in table 2.
[table 2]
As shown in Table 2, when using the decomposition accelerating agent of the embodiment 8 ~ 14 containing (1) ~ (3) composition, the number of days decomposed completely to vinyl chloride class is less than 31 days, relative to this, comparative example 4 not containing (1) composition is 48 days, comparative example 5 not containing (2) composition is 45 days, and the comparative example 6 not containing (3) composition is 40 days, learns that decomposition rate is extremely low.
It should be noted that, when not using decomposition accelerating agent, (comparative example 7) be not even if also complete in the decomposition of the 100th day vinyl chloride class.
In addition, relatively as (2) composition use skimmed milk power and/or yeast extract embodiment 9,11,12 known, use the decomposition rate of the embodiment 9 of skimmed milk power higher than the embodiment 11 only using yeast extract, the decomposition rate combinationally using the embodiment 12 of skimmed milk power and yeast extract is the highest.
It should be noted that, more various change the content of vitamin B12 embodiment 9,13,14 known, if vitamin B12 relative to the compounding amount of glycerine 1 mass parts in the scope of 0.00001 ~ 0.001 mass parts; decomposition rate could not produce difference.
(embodiment 15)
Assuming that by vinyl chloride class contaminated land, carry out decomposition run by following method.
In 1L capacity screw top jar, put into from the soil 700g taked by trichloro-ethylene contaminated land, the underground water 300g that takes from identical place, after adding above-mentioned bacterium liquid 5mL, add after decomposition accelerating agent E 0.5g is dissolved in 50mL distilled water, after nitrogen displacement, in the dark carry out quiescent culture under room temperature.Regularly by the concentration of vinyl chloride class (trichloro-ethylene, c-DCE, VC) in gas chromatography determination headroom and the concentration of ethene.Vinyl chloride class headed by the trichloro-ethylene comprised in Polluted Soil and underground water all became environmental benchmark value (trichloro-ethylene=0.03mg/l, dichloroethylene=0.04mg/l, VC=0.002mg/l) below afterwards at the 150th day.Result is shown in Fig. 7.
The decomposition experiment 3> of < vinyl chloride class
(evaluation method 3 of decomposition accelerating agent)
The making > of < bacterium liquid
The culture medium 50mL adding yeast extract in the mode of 0.1g/L in above-mentioned mineral matter basal medium is taken to 100mL volumetric glass bottle, after nitrogen displacement, after utilizing autoclave to carry out sterilization treatment, add the underground water 25mL from being taked by tetrachloro-ethylene (PCE) contaminated soil, after nitrogen displacement, enclose hydrogen 2.5mL and PCE 0.46 μ L (being equivalent to 10mg/L), dark place quiescent culture at 20 DEG C.Vinyl chloride class in results of regular determination headroom, takes 1mL in the moment not detecting vinyl chloride class, in the mineral matter basal medium 75mL that the autoclaving continuing to be seeded to interpolation yeast extract 0.1g/L is crossed.Using carrying out this material again cultivating 3 times as " bacterium liquid ", for the decomposition experiment of following vinyl chloride class.
(embodiment 16 ~ 18)
Assuming that the underground water polluted by vinyl chloride class, carry out decomposition run by following method.
Above-mentioned mineral matter basal medium 75ml is taken in the bottle of glass 100ml capacity, the equal amount of mixture (embodiment 18) of above-mentioned decomposition accelerating agent A (embodiment 16), above-mentioned decomposition accelerating agent G (embodiment 17), above-mentioned decomposition accelerating agent A and above-mentioned decomposition accelerating agent G is added respectively in the mode of 0.2g/L, after nitrogen displacement, autoclave is utilized to carry out sterilization treatment.After cooling, add above-mentioned bacterium liquid 1.5ml, after nitrogen displacement, enclose tetrachloro-ethylene (PCE) in the mode of 10 μ g/ml.
At 20 DEG C, this bottle is carried out quiescent culture.After 0 day, 3 days, 10 days, 18 days, 24 days, 36 days, 45 days, 49 days, 59 days, 66 days, 75 days, 84 days, 87 days, by the various vinyl chloride classes in the headroom of gas chromatography determination bottle, namely PCE, TCE, c-DCE, t-DCE, 1,1-DCE, VC content and ethylene contents.
For experimental result, by the content of vinyl chloride class until become below groundwater environment a reference value, namely PCE becomes below 0.01mg/L, TCE becomes below 0.03mg/L, cDCE and t-DCE becomes below 0.04mg/L, 1, the number of days in the moment that 1-DCE becomes below 0.02mg/L, VC becomes below 0.002mg/L, as " number of days to required for decomposition ", is shown in table 3.
In addition, consider that the activation of microorganism is in initial generation, therefore the reduction of every 1 day of PCE content of near 18th day is shown in table 3 as initial decomposition speed.
[table 3]
Claims (9)
1. a decomposition accelerating agent for volatility organohalogen compound, is characterized in that, its contain in following (A) ~ (C) a kind or two or more,
(A) fruit of citrus or the extract that obtained by this fruit
(B) pericarp of citrus or the extract that obtained by this pericarp
(C) containing the blend that following (1) ~ (3) are whole
(1) glycerine
(2) lactoprotein and/or yeast extract
(3) vitamin B12.
2. the decomposition accelerating agent of volatility organohalogen compound according to claim 1, wherein, decomposition accelerating agent contains (A) and in (B) at least a kind time, described extract is the extract obtained using water as solvent.
3. decomposition accelerating agent according to claim 1, wherein, when decomposition accelerating agent contains (C), relative to glycerine 1 mass parts of described (1), containing lactoprotein and/or the yeast extract of counting (2) described in 0.1 ~ 3 mass parts with solid constituent.
4. decomposition accelerating agent according to claim 1 and 2, wherein, when decomposition accelerating agent contains (C), relative to glycerine 1 mass parts of described (1), the vitamin B12 containing (3) described in 0.00001 ~ 0.001 mass parts.
5. a decomposition accelerating agent composition for volatility organohalogen compound, is characterized in that, it contains decomposition accelerating agent according to claim 1 as active ingredient.
6. one kind utilizes microorganism to promote the method that volatility organohalogen compound decomposes, it is characterized in that, make decomposition accelerating agent according to claim 1 or decomposition accelerating agent composition according to claim 5 and the soil and/or the groundwater contacts that comprise volatility organohalogen compound.
7. method according to claim 6, wherein, volatility organohalogen compound is organochlorine based compound.
8. method according to claim 7, wherein, organochlorine based compound is for being selected from by carbon tetrachloride, chloroform, carrene, monochloro methane, 1,2-dichloroethanes, 1,1-dichloroethylene, cis-1,2-dichloroethylene, anti-form-1,2-dichloroethylene, 1,3-dichloropropylene, tetrachloro-ethylene, 1,1, at least a kind in the group of 1-trichloroethanes, 1,1,2-trichloroethanes, trichloro-ethylene, vinyl chloride composition.
9. method according to claim 6, wherein, microorganism be selected from intend Coccus bacterium by Clostridia bacteria, dehalogenate Bacillus bacteria, dehalogenation, in group that dehalogenation Spirillum bacterium, Desulfobacter bacterium, Desulfomonas bacterium, desulfurization Mycotoruloides bacterium form at least a kind.
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| PCT/JP2013/061334 WO2013157556A1 (en) | 2012-04-18 | 2013-04-16 | Decomposition accelerator for volatile organic halogen compound |
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| CN104801536A (en) * | 2015-04-15 | 2015-07-29 | 刘骁勇 | Method for remedying halohydrocarbon contaminated site through combination of chemical leaching and microorganisms |
| CN106587342A (en) * | 2016-12-29 | 2017-04-26 | 中国科学院城市环境研究所 | Bioremediation reagent and application thereof in removing 1,2-dichloroethane in composite polluted water body |
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| JP7049612B2 (en) * | 2017-02-17 | 2022-04-07 | シナプテック株式会社 | Manufacturing method of VOC decomposition accelerator for soil improvement |
| JP2018175529A (en) * | 2017-04-17 | 2018-11-15 | 東急建設株式会社 | Decomposition accelerator, and environmental cleanup method using the decomposition accelerator |
| JP7505340B2 (en) | 2020-09-07 | 2024-06-25 | 栗田工業株式会社 | Decomposition promoter and method for decomposing volatile organic halogen compounds |
| TWI774052B (en) * | 2020-09-08 | 2022-08-11 | 財團法人工業技術研究院 | Novel dehalococcoides sp., mixed consortium having a dechlorination effect, microbial preparation containing the mixed consortium, dechlorination method for chlorinated hydrocarbons and bioremediation method by the microbial preparation |
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| CN106587342A (en) * | 2016-12-29 | 2017-04-26 | 中国科学院城市环境研究所 | Bioremediation reagent and application thereof in removing 1,2-dichloroethane in composite polluted water body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013157556A1 (en) | 2015-12-21 |
| JP6126588B2 (en) | 2017-05-10 |
| TW201402242A (en) | 2014-01-16 |
| CN104411370B (en) | 2018-02-02 |
| WO2013157556A1 (en) | 2013-10-24 |
| TWI594815B (en) | 2017-08-11 |
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