JP5244296B2 - Permeability purification wall and purification method of contaminated groundwater - Google Patents
Permeability purification wall and purification method of contaminated groundwater Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、有機化合物に汚染した水、特に地下水に用いられる透水性浄化壁及び地下水の浄化処理方法に関する。 The present invention relates to a water-permeable purification wall used for water contaminated with an organic compound, particularly groundwater, and a method for purifying groundwater.
工場や給油施設等から石油留分等の有機化合物が漏洩した場合、地下地盤に染込み、土壌汚染を引き起こすことがある。この汚染有機化合物には水に溶解する物質（例えば石油留分においてはベンゼン、トルエン、キシレン等）が含まれていることもあり、汚染土壌領域から降雨等により有機化合物が流出し、地下水を汚染することや、さらに汚染された地下水が帯水層によって広範囲に拡散することが懸念される。 If organic compounds such as petroleum fractions leak from factories or refueling facilities, they may infiltrate the underground ground and cause soil contamination. These polluted organic compounds may contain substances that dissolve in water (for example, benzene, toluene, xylene, etc. in petroleum fractions), and organic compounds will flow out of the contaminated soil area due to rainfall, etc., contaminating groundwater. There is also a concern that contaminated groundwater will be diffused extensively by the aquifer.
このような有機化合物により汚染された地下水の原位置浄化方法の１つとして、汚染地下水領域の流向下流側に浄化ゾーン（浄化壁）を不透水層に達するように設けて、この浄化ゾーンを通過させることで汚染地下水を浄化する浄化壁工法が知られている。浄化壁工法としては、汚染対象物質を浄化壁中の微生物の分解活性を利用して分解する方法（特許文献１参照。）等や、汚染対象物質を鉄紛等の還元剤等を用いて分解する方法（特許文献２参照。）等や、これらを併用する方法（特許文献３参照。）等が知られている。 As one of the methods for in-situ purification of groundwater contaminated with organic compounds, a purification zone (purification wall) is provided to reach the impermeable layer on the downstream side of the contaminated groundwater area, and passes through this purification zone. A purification wall construction method is known that purifies contaminated groundwater. As a purification wall method, a method of decomposing a target substance to be contaminated by utilizing the decomposition activity of microorganisms in the purification wall (see Patent Document 1) or the like, or a target substance to be contaminated is decomposed using a reducing agent such as iron powder. And the like (see Patent Document 2) and the like, and the method of using them together (see Patent Document 3) are known.
ところで、微生物による浄化壁工法は、浄化壁中に含まれる微生物を増殖・活性化し、この微生物を汚染物質の分解に利用する方法である。この浄化壁中の微生物の増殖・活性化方法としては、従来から、効率的な酸素や栄養塩の供給、微生物増殖の場となりうるゼオライトやベントナイト等の多孔質担体の配合、土着微生物以外の微生物の添加等の手法が検討されているが、これらの方法による浄化能力は未だ十分満足できるものではない。
本発明の目的は、石油留分等の有機化合物により汚染された地下水の、より効率的な浄化処理を提供することにある。 An object of the present invention is to provide a more efficient purification treatment of groundwater contaminated with organic compounds such as petroleum fractions.
そこで、本発明者らは鋭意検討した結果、汚染有機化合物を分解する微生物が存在する現地土壌に貝殻を配合した透水性浄化壁を用いると、浄化壁中の微生物増殖効果が飛躍的に向上し、汚染水に含有する有機化合物の分解活性も向上することを見出し、本発明を完成するに至った。
すなわち、本発明は、有機化合物で汚染された水を、該有機化合物を分解する微生物の含有する土壌を用いて浄化する透水性浄化壁において、該微生物が存在する土壌に貝殻を含有せしめたことを特徴とする、透水性浄化壁を提供するものである。
また、本発明は、有機化合物に汚染された地下水を上記透水性浄化壁に通過させることを特徴とする、有機化合物に汚染された地下水の浄化処理方法を提供するものである。
Therefore, as a result of intensive studies, the present inventors have dramatically improved the effect of microbial growth in the purification wall by using a water-permeable purification wall containing shells in the local soil where microorganisms that decompose contaminating organic compounds exist. The inventors have found that the decomposition activity of organic compounds contained in contaminated water is also improved, and have completed the present invention.
That is, the present invention is a water-permeable purification wall that purifies water contaminated with an organic compound using soil containing a microorganism that decomposes the organic compound, and includes a shell in the soil where the microorganism exists. The water-permeable purification | cleaning wall characterized by these is provided.
The present invention also provides a method for purifying groundwater contaminated with an organic compound, characterized in that groundwater contaminated with an organic compound is passed through the water-permeable purification wall.
本発明によれば、浄化壁中の微生物増殖効果が向上し、汚染有機化合物の分解活性も向上することにより、有機化合物に汚染された地下水の浄化又は汚染領域の拡散防止をすることができる。 ADVANTAGE OF THE INVENTION According to this invention, the microorganisms proliferation effect in a purification | cleaning wall improves, and the decomposition | disassembly activity of a contaminated organic compound can also be improved, and the purification | cleaning of the groundwater contaminated with the organic compound or the diffusion prevention of a contaminated area | region can be performed.
本発明における透水性浄化壁は、汚染された地下水に含まれる有機化合物を分解することができる微生物を含有する土壌に貝殻を含有させたものである。
本発明における浄化壁は、土壌に貝殻を配合して混合したものが好ましいが、汚染水の流向に直交する向きに複数の層を形成したものでもよい。
The water-permeable purification wall in the present invention is obtained by containing shells in soil containing microorganisms capable of decomposing organic compounds contained in contaminated groundwater.
The purification wall in the present invention is preferably a mixture of sea shells mixed with soil, but it may be one in which a plurality of layers are formed in a direction perpendicular to the direction of contaminated water flow.
本発明の浄化壁の成分の１つである土壌は、汚染された地下水に含まれる対象となる有機化合物を分解する微生物を含有するものである。
本発明で用いる土壌は、対象とする有機化合物を分解する公知の微生物を土壌に配合し、調製したものでもよいが、現地の汚染土壌領域には対象とする有機化合物を分解する微生物の存在の可能性が高いため、現地の汚染土壌領域の土壌を用いるのが好ましい。また、現地汚染土壌領域に存在する汚染対象有機化合物を分解する微生物を抽出し、増殖させたものを現地の汚染土壌領域の土壌または別の土壌に配合し、調製したものでもよい。
Soil, which is one of the components of the purification wall of the present invention, contains microorganisms that decompose organic compounds to be contained in contaminated groundwater.
The soil used in the present invention may be prepared by blending and preparing known microorganisms that decompose the target organic compounds in the soil, but the presence of microorganisms that decompose the target organic compounds in the local contaminated soil region. Because of the high possibility, it is preferable to use soil in the local contaminated soil area. Moreover, the microorganism which decomposes | disassembles the organic compound to be contaminated which exists in a local contaminated soil area | region was extracted, and what was propagated may mix | blend with the soil of the local contaminated soil area | region, or another soil, and may prepare.
本発明の浄化壁の成分の１つである貝殻は、海水、淡水、又は汽水領域中の生息する貝類又はその貝殻のいずれのものでも良い。当該貝類としては、例えば、ホタテ貝、カキ貝、ホッキ貝、アコヤ貝、クロチョウ貝、アサリ、シジミ、ハマグリ、アオヤギ、カラス貝、サザエ、及びミル貝等が挙げられ、これら貝殻を１種類又は２種類以上混合して用いても良い。好ましくは貝類の加工工場や産業廃棄処理場等で大量且つ定常的に入手できる貝殻であり、より好ましくはホタテ貝殻やカキ貝殻であり、特に好ましいものはホタテ貝殻である。また、貝類に付着している身等の成分を除去するために、煮沸又は焼成等熱処理を行ってもよい。 The shell which is one of the components of the purification wall of the present invention may be any of the shellfish or its shell inhabiting seawater, fresh water, or brackish water. Examples of the shellfish include scallops, oysters, oysters, pearl oysters, black scallops, clams, swordfish, clams, blue goats, crows, turban shells, mill shells, and the like. A mixture of two or more types may be used. Preferred are shells that can be obtained regularly and in large quantities in shellfish processing factories, industrial waste treatment plants, etc., more preferred are scallop shells and oyster shells, and particularly preferred are scallop shells. Further, heat treatment such as boiling or baking may be performed in order to remove components such as body attached to shellfish.
本発明の浄化壁に用いる土壌の粒径は、特に限定されないが、貝殻を配合した際に適度な透水性を有することと施工性を考慮し選択することが好ましい。
本発明の浄化壁に用いる貝殻の粒径は、微生物の存在する土壌に接し易いように適当なサイズに貝殻を粉砕して用いることが好ましい。粉砕した貝殻の粒径は特に限定されないが、本発明に用いる土壌よりも粗い粒径であることが透水性を高める観点から好ましい。好ましくは平均粒径０.５ｍｍ〜５０ｍｍであり、より好ましくは１ｍｍ〜３０ｍｍであり、特に好ましくは１ｍｍ〜２０ｍｍである。
The particle size of the soil used for the purification wall of the present invention is not particularly limited, but is preferably selected in consideration of having appropriate water permeability and workability when shells are blended.
As for the particle diameter of the shell used for the purification wall of the present invention, the shell is preferably pulverized to an appropriate size so as to be easily in contact with the soil in which microorganisms are present. The particle size of the crushed shell is not particularly limited, but a particle size coarser than the soil used in the present invention is preferable from the viewpoint of increasing water permeability. The average particle size is preferably 0.5 mm to 50 mm, more preferably 1 mm to 30 mm, and particularly preferably 1 mm to 20 mm.
本発明の浄化壁に用いる貝殻の浄化壁への配合容量％は、微生物が汚染した有機化合物の十分な分解能を得、有機化合物浄化開始当初から十分な分解能を有する微生物量を確保する必要があるため、浄化壁全容量に対して１０〜８０容量％を配合することが好ましく、１５〜７５容量％がより好ましく、２０〜７０容量％が特に好ましい。 The mixing volume% of the shell used for the purification wall of the present invention needs to obtain a sufficient resolution of the organic compound contaminated with microorganisms and ensure a sufficient amount of microorganisms from the beginning of the purification of the organic compound. Therefore, it is preferable to mix 10 to 80% by volume with respect to the total purification wall volume, more preferably 15 to 75% by volume, and particularly preferably 20 to 70% by volume.
本発明における浄化壁の適度な透水性を得るため、本発明に用いる土壌及び貝殻の他に、これらより粒径の大きい、ケイ砂、川砂、砂利、砕石等を１種又は２種以上を混合してもよい。 In order to obtain an appropriate water permeability of the purification wall in the present invention, in addition to the soil and shell used in the present invention, one or more kinds of silica sand, river sand, gravel, crushed stone, etc. having a particle size larger than these are mixed. May be.
本発明における浄化壁により浄化対象となる有機化合物は、地下水により汚染拡大するような物質であればどのような物質でも対象となり、例えば炭化水素系化合物や含酸素化合物等が挙げられる。特に、石油留分に含まれ、地下水への溶解性が比較的高いベンゼン、トルエン、キシレン等が好ましい。 As the organic compound to be purified by the purification wall in the present invention, any substance can be used as long as it is a substance that expands contamination by groundwater, and examples thereof include hydrocarbon compounds and oxygen-containing compounds. In particular, benzene, toluene, xylene and the like which are contained in the petroleum fraction and have relatively high solubility in groundwater are preferable.
本発明の浄化壁には、微生物が生育に使用する栄養成分を添加してもよく、当該栄養成分としては、一般的に土壌に含まれる窒素源、リン源、ミネラル成分等で十分であるが、地下水中や現地土壌中に充分量の栄養塩成分が少ない又は存在しない場合には、これら栄養塩成分を浄化壁に混合することが好ましい。この混合方法としては、特に限定されないが、例えば、後述する浄化壁施工時又は後の際には、透水性浄化壁中にボーリング穴や井戸を掘ってそこから適宜栄養塩を添加・追加する方法、栄養塩成分の徐放性を高くしたものを土壌等に配合する方法等が挙げられる。
窒素、リンおよびカリウムの栄養塩成分を浄化壁に添加する場合には、対象汚染物質の有機化合物に由来する炭素原子に対するモル比換算で、窒素原子が１／１０００〜１／１０、リン原子が１／１０００〜５／１００、カリウム原子が１／１０００〜１／１００とすることが好ましい。
The purifying wall of the present invention may be added with nutrients used by microorganisms for growth. As the nutrient components, nitrogen sources, phosphorus sources, mineral components, etc., generally contained in soil are sufficient. When there is little or no sufficient amount of nutrient components in the groundwater or the local soil, it is preferable to mix these nutrient components with the purification wall. The mixing method is not particularly limited. For example, when the purification wall described later is used or after, a method of adding / adding a nutrient salt appropriately from the bored hole or well in the permeable purification wall. And a method of blending a soil or the like with a high sustained release property of a nutrient component.
When adding nutrient components of nitrogen, phosphorus and potassium to the purification wall, the nitrogen atom is 1/1000 to 1/10 and the phosphorus atom is converted into a molar ratio with respect to the carbon atom derived from the organic compound of the target pollutant. 1/1000 to 5/100 and potassium atoms are preferably 1/1000 to 1/100.
本発明における浄化壁中の地下水のｐＨは、有機化合物の分解に用いる微生物の生育阻害が生じないｐＨ付近であれば特に調整しなくともよいが、汚染水が微生物の生育や有機化合物分解能に影響を与えるような酸性又は塩基性物質を有する場合は、中和剤としてアルカリ処理剤又は酸処理剤を配合して調整することが好ましい。好ましいｐＨの範囲は５〜１０であり、より好ましいｐＨは６〜９である。 The pH of the groundwater in the purification wall in the present invention does not need to be adjusted as long as it is around pH that does not inhibit the growth of microorganisms used for decomposing organic compounds, but contaminated water affects the growth of microorganisms and the resolution of organic compounds. In the case of having an acidic or basic substance that gives an acid, it is preferable to adjust by adding an alkali treating agent or an acid treating agent as a neutralizing agent. A preferable pH range is 5 to 10, and a more preferable pH is 6 to 9.
本発明における浄化壁に用いる微生物に、微生物の増殖及び有機化合物分解効率を高めるため、適宜酸素を供給することが好ましい。当該供給する酸素量（濃度）は、水（地下水）に溶存している有機化合物の濃度や溶存酸素濃度及び汚染水（汚染地下水）流速等の条件により決められる。例えば、地下水の溶存酸素濃度は、０．５ｍｇ／Ｌ〜飽和が好ましく、より浄化率を高めるため１ｍｇ／Ｌ以上がより好ましく、１．５ｍｇ／Ｌ以上が特に好ましい。
酸素の供給方法としては、浄化壁中のｐＨを急激に変化させなければどのような方法で供給しても良いが、具体的には酸素徐放剤により供給する方法、空気を直接供給する方法、またはこれらを併用する方法等が挙げられる。
In order to increase the growth of microorganisms and the decomposition efficiency of organic compounds, it is preferable to appropriately supply oxygen to the microorganisms used for the purification wall in the present invention. The amount (concentration) of oxygen to be supplied is determined by conditions such as the concentration of organic compounds dissolved in water (groundwater), the dissolved oxygen concentration, and the flow rate of contaminated water (contaminated groundwater). For example, the dissolved oxygen concentration of groundwater is preferably 0.5 mg / L to saturation, more preferably 1 mg / L or more, and particularly preferably 1.5 mg / L or more in order to further increase the purification rate.
As a method of supplying oxygen, any method may be used as long as the pH in the purification wall is not changed rapidly. Specifically, a method of supplying with an oxygen sustained-release agent, a method of supplying air directly Or a method using these in combination.
酸素徐放剤としては、金属過酸化物が好ましく、より好ましくは水と反応して酸素を発生する過酸化マグネシウムや過酸化カルシウム等が挙げられる。
酸素徐放剤は、透水性浄化壁施工時に浄化壁に混合することが一般的であるが、長期間、浄化を実施する場合には酸素放出量が徐々に低下することがあるため、随時追加することが好ましい。このときの追加方法としては、酸素徐放剤のスラリーを透水性浄化壁中に形成したボーリング穴から圧入する方法や、透水性浄化壁中に設けた井戸から酸素徐放剤を供給する方法がある。
本発明の浄化壁に用いる酸素徐放剤の配合容量は、例えば、過酸化マグネシウムや過酸化カルシウム等の過酸化物が酸素徐放剤に２５〜３５質量％含まれる場合には、経済性及び地下水中の溶存酸素の飽和の状態から浄化壁全容量に対し０．１〜３容量％の混合割合が有効である。より好ましくは、地下水中の溶存酸素の飽和があるため０．１〜２容量％程度である。
As the oxygen sustained-release agent, metal peroxide is preferable, and magnesium peroxide, calcium peroxide, etc. that react with water to generate oxygen are preferable.
Oxygen sustained-release agents are generally mixed with the purification wall during the construction of the water-permeable purification wall. However, when purification is performed for a long period of time, the oxygen release amount may gradually decrease. It is preferable to do. As an additional method at this time, there are a method of press-fitting a slurry of an oxygen sustained-release agent from a boring hole formed in the water-permeable purification wall, and a method of supplying the oxygen sustained-release agent from a well provided in the water-permeable purification wall. is there.
The compounding capacity of the oxygen sustained-release agent used for the purification wall of the present invention is, for example, economical when the peroxide such as magnesium peroxide and calcium peroxide is contained in the oxygen sustained-release agent in an amount of 25 to 35% by mass. From the saturated state of dissolved oxygen in the groundwater, a mixing ratio of 0.1 to 3% by volume with respect to the total capacity of the purification wall is effective. More preferably, it is about 0.1 to 2% by volume because there is saturation of dissolved oxygen in the groundwater.
空気（酸素）を直接供給する方法としては、例えば、ブロアーを設けて透水性浄化壁中もしく浄化壁の手前の地下水へ直接供給する手段等が挙げられる。 As a method for directly supplying air (oxygen), for example, there is a means for providing a blower to directly supply air into the permeable purification wall or underground water before the purification wall.
本発明における透水性浄化壁は、汚染地下水領域の流向下流側を掘削し、上述した浄化壁（透水性浄化壁成分）を汚染地下水深度より深い位置または不透水層まで充填（埋設）した浄化ゾーン（壁）である。
透水性浄化壁施工方法および透水性浄化壁の形状は、特に拘らないが、地下水流向に対して垂直に延ばした壁状もしくは円弧の一部が重なるように円柱状に配した複数の柱状体群からなる。また、汚染水を透水性浄化壁に誘導しやすくするために、透水性浄化壁の左右両サイド周辺に地下水流向に対して拡開する止水壁を設けても良い。
地下水流向に対する透水性浄化壁の層厚は、汚染地下水中の有機化合物の濃度と地下水流速等の条件にもよるが、０．１ｍ〜１０ｍ、より好ましくは０.５ｍ〜５ｍ程度である。
The permeable purification wall in the present invention is a purification zone obtained by excavating the flow direction downstream side of the contaminated groundwater region and filling (embedding) the above-described purification wall (permeable permeable purification wall component) to a position deeper than the contaminated groundwater depth or an impermeable layer. (Wall).
The method of constructing the water-permeable purification wall and the shape of the water-permeable purification wall are not particularly limited, but a plurality of columnar bodies arranged in a columnar shape so that a wall shape extending perpendicularly to the direction of groundwater flow or a part of an arc overlaps each other. Consists of. Further, in order to easily guide the contaminated water to the water permeable purification wall, a water stop wall that expands with respect to the direction of the groundwater flow may be provided around the left and right sides of the water permeable purification wall.
The layer thickness of the water-permeable purification wall with respect to the direction of groundwater flow is 0.1 m to 10 m, more preferably about 0.5 m to 5 m, although it depends on conditions such as the concentration of organic compounds in the contaminated groundwater and the groundwater flow velocity.
本発明における有機化合物汚染地下水の浄化処理方法は、有機化合物に汚染された地下水を形成した該透水性浄化壁に通過させることにより土壌に存在する微生物に有機化合物を分解させ、浄化するものである。
透水性浄化壁を通過させる汚染地下水の速度は、透水性浄化壁の層厚や微生物における有機化合物の分解能にもよるが、地下水の流速を維持することが好ましい。より好ましくは１〜１００ｃｍ／日であり、特に好ましくは３〜５０ｃｍ／日である。
The method for purifying organic compound-contaminated groundwater in the present invention is to decompose and purify the organic compound by microorganisms present in the soil by passing through the water-permeable purification wall formed with the groundwater contaminated with the organic compound. .
The speed of the contaminated groundwater that passes through the permeable purification wall depends on the layer thickness of the permeable purification wall and the resolution of organic compounds in microorganisms, but it is preferable to maintain the flow rate of the groundwater. More preferably, it is 1-100 cm / day, Most preferably, it is 3-50 cm / day.
次に実施例及び比較例を挙げて本発明をさらに具体的に説明する。
＜実施例１＞
土壌（砂質土）に１ｍｍ〜３ｍｍの粒子サイズに破砕したホタテ貝殻を等容量比で均一混合した供試体をガラスカラム（内径５ｃｍ，長さ２０ｃｍ）に充填した。
このとき、当該土壌は石油精製施設の土壌より採取し、供試体全容量に対してホタテ貝殻５０容量％となるようにホタテ貝殻を配合し、できるだけ均一となるように混合したものを、ホタテ５０％混合土壌とした。
充填したカラムに、ベンゼン（Ｂ）、トルエン（Ｔ）およびキシレン（Ｘ）の混合物を飽和状態に酸素を溶存させた水に５ｍｇ／Ｌ（Ｂ、ＴおよびＸの溶存比は、質量比でＢ：Ｔ：Ｘ＝１：８：１）の濃度で溶解させたものを原水として、流速３０ｃｍ／日の速さで垂直に立てたカラムにアップフローで通過させ、カラム出口の処理水を採取し、処理水中のＢＴＸ濃度をヘッドスペース-ガスクロマトグラフ質量分析法（平成９年環告１０号 ＪＩＳ Ｋ０１２５ ５.２）により測定した。結果を図１に示した。
なお、図中の浄化率の定義は以下に示すとおりである。
浄化率（％）＝〔（原水ＢＴＸ濃度−処理水ＢＴＸ濃度）／原水ＢＴＸ濃度〕×１００
Next, the present invention will be described more specifically with reference to examples and comparative examples.
<Example 1>
A glass column (inner diameter: 5 cm, length: 20 cm) was packed with a specimen in which scallop shells crushed to a particle size of 1 mm to 3 mm were uniformly mixed with soil (sandy soil) at an equal volume ratio.
At this time, the soil is collected from the soil of an oil refining facility, and scallop shells are blended so that the volume of scallop shells is 50% by volume with respect to the total volume of the specimen, and mixed so as to be as uniform as possible. % Mixed soil.
In a packed column, a mixture of benzene (B), toluene (T) and xylene (X) is dissolved in water in which oxygen is dissolved in a saturated state at 5 mg / L (the dissolution ratio of B, T, and X is B by mass ratio). : T: X = 1: 8: 1) dissolved in raw water is passed up-flow through a vertical column at a flow rate of 30 cm / day, and the treated water at the column outlet is collected. The BTX concentration in the treated water was measured by headspace-gas chromatograph mass spectrometry (1997 Circular 10 JIS K0125 5.2). The results are shown in FIG.
The definition of the purification rate in the figure is as shown below.
Purification rate (%) = [(raw water BTX concentration−treated water BTX concentration) / raw water BTX concentration] × 100
＜比較例１＞
ガラスカラムに充填した供試体を土壌（砂質土）のみとした他は実施例１と同じ条件で実施した。結果を図１に示した。
<Comparative Example 1>
The test was carried out under the same conditions as in Example 1 except that the specimen filled in the glass column was only soil (sandy soil). The results are shown in FIG.
＜実施例２＞
原水に溶解させるベンゼン（Ｂ）、トルエン（Ｔ）およびキシレン（Ｘ）の混合物の濃度を１０ｍｇ／Ｌ（Ｂ、ＴおよびＸの溶存比は、質量比でＢ：Ｔ：Ｘ＝１：８：１）とした他は、実施例１と同じ条件で実施した。結果を図２に示した。
<Example 2>
The concentration of the mixture of benzene (B), toluene (T) and xylene (X) dissolved in raw water is 10 mg / L (the dissolution ratio of B, T and X is B: T: X = 1: 8: The process was performed under the same conditions as in Example 1 except for 1). The results are shown in FIG.
また、カラム出口の溶存酸素濃度をエイブル株式会社製溶存酸素計（溶存酸素電極（型式ＳＯ−Ｐ）と溶存酸素指示計（型式ＤＭ−１０３２）で構成）を用いて測定した。このとき、原水溶存酸素濃度８ｍｇ／Ｌ、原水ＢＴＸ濃度１０ｍｇ／Ｌである。結果を表１に示した。 In addition, the dissolved oxygen concentration at the column outlet was measured using a dissolved oxygen meter (configured by a dissolved oxygen electrode (model SO-P) and a dissolved oxygen indicator (model DM-1032)) manufactured by Able Co., Ltd. At this time, the raw water-existing oxygen concentration is 8 mg / L and the raw water BTX concentration is 10 mg / L. The results are shown in Table 1.
＜比較例２＞
ガラスカラムに充填した供試体を土壌（砂質土）とした他は、実施例２と同じ条件で実施した。結果をそれぞれ図２及び表１に示した。
<Comparative example 2>
The test was carried out under the same conditions as in Example 2 except that the specimen filled in the glass column was soil (sandy soil). The results are shown in FIG. 2 and Table 1, respectively.
＜実施例３＞
ガラスカラムに充填した供試体を土壌（砂質土）に１ｍｍ〜３ｍｍの粒子サイズに破砕したホタテ貝殻を等容量比で混ぜたものにさらに酸素徐放剤（リジェネシス社製ＯＲＣ、過酸化マグネシウム成分２５〜３５質量％含有）を供試体の容量に対し、１．０容量％を入れて均一混合したものを用いた他は、実施例２と同じ条件で実施した。結果を図３に示した。
<Example 3>
A test sample packed in a glass column was mixed with an equal volume ratio of scallop shells crushed to a particle size of 1 mm to 3 mm in soil (sandy soil), and an oxygen controlled release agent (ORC, Regenesis ORC, magnesium peroxide) The component was contained under the same conditions as in Example 2 except that 1.0% by volume was added to the volume of the specimen and uniformly mixed. The results are shown in FIG.
＜比較例３＞
ガラスカラムに充填した供試体を土壌（砂質土）に酸素徐放剤（リジェネシス社製ＯＲＣ、過酸化マグネシウム成分２５〜３５質量％含有）を供試体の容量に対し、１．０容量％を入れて均一混合したものを用いた他は、実施例３と同じ条件で実施した。結果を図３に示した。
<Comparative Example 3>
Specimen packed in a glass column is soiled (sandy soil) with an oxygen sustained release agent (ORC manufactured by Regenesis, containing 25 to 35% by mass of magnesium peroxide component) at 1.0% by volume with respect to the volume of the specimen. Example 3 was carried out under the same conditions as in Example 3 except that a homogeneous mixture was used. The results are shown in FIG.
＜実施例４＞
貝殻のＢＴＸ吸着作用を検討するため、本実施例で使用した土壌微生物の生育に適さない環境下においてカラム試験を行った。原水をアルカリ性（ｐＨ１０．５）に調整した他は、実施例２と同じ条件で実施した。結果を表２に示した。なお、実施例４は参考例である。
<Example 4>
In order to examine the BTX adsorption action of the shell, a column test was performed in an environment unsuitable for the growth of the soil microorganisms used in this example. The test was carried out under the same conditions as in Example 2 except that the raw water was adjusted to be alkaline (pH 10.5). The results are shown in Table 2. Example 4 is a reference example.
表１に示すように、ホタテ貝殻を配合したカラム（実施例２）は土壌のみのカラム（比較例２）よりも、多く酸素が消費されており、カラム内で微生物が活し、増殖していることがわかる。さらに、図１に示すように、ホタテ貝殻を含有することによって、土壌に存在する微生物におけるＢＴＸの有機化合物の分解が認められた。
また、表２に示すように、原水のＢＴＸ濃度はカラム処理前の入口と処理後の出口ともほぼ同一の濃度を示し、ホタテ貝殻のみのＢＴＸの吸着能は認められなかった。
表１及び２より、ホタテ貝殻によるＢＴＸ分解促進効果は吸着作用によるものではなく、微生物の活性化によるものであることが明らかである。
さらに、図２及び図３に示すように、酸素徐放剤を添加することによって微生物がより活性化し、ＢＴＸの有機化合物の分解が促進されたことが認められた。
As shown in Table 1, the column containing the scallop shell (Example 2) consumes more oxygen than the soil-only column (Comparative Example 2), and microorganisms are activated and proliferated in the column. I understand that. Furthermore, as shown in FIG. 1, the decomposition | disassembly of the organic compound of BTX in the microorganisms which exist in soil was recognized by containing a scallop shell.
In addition, as shown in Table 2, the BTX concentration of the raw water was almost the same at the inlet before the column treatment and the outlet after the treatment, and the adsorption ability of BTX only in the scallop shell was not recognized.
From Tables 1 and 2, it is clear that the BTX degradation promoting effect by the scallop shell is not due to the adsorption action but due to the activation of the microorganisms.
Furthermore, as shown in FIG.2 and FIG.3, it was recognized by adding an oxygen sustained release agent that the microorganism was activated more and the decomposition | disassembly of the organic compound of BTX was accelerated | stimulated.
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| JP5244321B2 (en) * | 2007-01-17 | 2013-07-24 | 一般財団法人石油エネルギー技術センター | Permeability purification wall and purification method of contaminated groundwater |
| JP5155619B2 (en) * | 2007-08-07 | 2013-03-06 | コスモ石油株式会社 | Soil and groundwater purification promoter and purification method |
| JP5374272B2 (en) * | 2009-08-03 | 2013-12-25 | 鹿島建設株式会社 | Purification system and purification method |
| JP5405936B2 (en) * | 2009-08-03 | 2014-02-05 | 鹿島建設株式会社 | Microbial purification method |
| JP5505047B2 (en) * | 2010-04-02 | 2014-05-28 | 株式会社Ｉｈｉ | Water purification method, water purification agent, and water purification agent manufacturing method |
| EP4202040A1 (en) * | 2010-07-01 | 2023-06-28 | Regenerative Research Foundation | Methods for culturing undifferentiated cells using sustained release compositions |
| CN106976961B (en) * | 2017-04-25 | 2023-07-21 | 农业部沼气科学研究所 | Aeration slow-release device |
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| JP4021511B2 (en) * | 1997-02-07 | 2007-12-12 | 株式会社荏原製作所 | Purification method for organic chlorine compound contaminants |
| JPS51117445A (en) * | 1975-04-07 | 1976-10-15 | Tamotsu Mori | Waste water disposal system making use of shells or crust aquatic crea tures |
| JPS60143898A (en) * | 1983-12-28 | 1985-07-30 | Agency Of Ind Science & Technol | Methane fermentation process |
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| JP3256857B2 (en) * | 1991-11-11 | 2002-02-18 | 日本ソリッド株式会社 | Environmental purification structure |
| JPH0671285A (en) * | 1992-08-28 | 1994-03-15 | Nippon Solid Co Ltd | Purification method for polluted water |
| JP2978404B2 (en) * | 1994-10-24 | 1999-11-15 | 富士車輌株式会社 | Wastewater purification equipment |
| JPH0938659A (en) * | 1995-07-31 | 1997-02-10 | Hiroshi Ono | Polluted water purifying system |
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| JP2000120061A (en) * | 1998-10-12 | 2000-04-25 | Seiko Kogyo Kk | Underground water purifying wall and its forming method |
| JP2001107333A (en) * | 1999-10-07 | 2001-04-17 | Fujita Corp | Poor oxygen water mass infiltration preventive method and poor oxygen water mass infiltration preventive fence |
| JP3724287B2 (en) * | 1999-11-09 | 2005-12-07 | 株式会社大林組 | Purification method of contaminated groundwater |
| JP2002233855A (en) * | 2001-02-06 | 2002-08-20 | Mikuniya Environmental Management Systems Institute Inc | Process and system for recovering shell as resource |
| JP2002370023A (en) * | 2001-04-10 | 2002-12-24 | Kawashima Hiroaki | Adsorbent and method for adsorbing pollutant |
| JP2003053355A (en) * | 2001-08-15 | 2003-02-25 | Shigeo Sakurai | Use of effect of mineral and system therefor |
| JP2004016859A (en) * | 2002-06-13 | 2004-01-22 | Kajima Corp | In situ purification method of polluted soil |
| JP2004066114A (en) * | 2002-08-07 | 2004-03-04 | Gc Kankyo Control Kk | Septic tank for sewage and system therefor |
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