TWI756791B - Colloidal composition and method for in situ remediation of hexavalent chromium - Google Patents
Colloidal composition and method for in situ remediation of hexavalent chromium Download PDFInfo
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本發明是關於一種整治六價鉻之組成物,特別是關於一種現地生物整治六價鉻之凝膠組成物及現地生物整治六價鉻之方法。 The present invention relates to a composition for rectifying hexavalent chromium, in particular to a gel composition for on-site biological rectification of hexavalent chromium and a method for on-site biological rectification of hexavalent chromium.
鉻是工業上重要的金屬元素,除了元素鉻之外,三價鉻及六價鉻化合物的使用範圍也相當廣泛,常用於電鍍、揉製、顏料、木材防朽及鋼鐵業等產業上。 Chromium is an important metal element in industry. In addition to elemental chromium, trivalent chromium and hexavalent chromium compounds are also widely used, and are often used in electroplating, kneading, pigments, wood anticorrosion and iron and steel industries.
然而,鉻的化合物具有毒性,其中又以鉻酸鹽及重鉻酸鹽等六價鉻化合物的毒性最強。六價鉻亦具有高刺激性。生物體在接觸及/或吸入六價鉻後,可能會引起皮膚、眼睛及/或呼吸道黏膜之過敏、發炎,甚至是潰瘍等不適。若不慎攝入六價鉻,容易造成嘔吐、胃痛等症狀,甚至造成腎臟及/或肝臟的損害,還可能引發肺癌及鼻竇癌等癌症。 However, chromium compounds are toxic, and hexavalent chromium compounds such as chromate and dichromate are the most toxic. Hexavalent chromium is also highly irritant. After exposure to and/or inhalation of hexavalent chromium, organisms may cause irritation, inflammation, and even ulcers of the skin, eyes and/or respiratory mucosa. Accidental ingestion of hexavalent chromium can easily cause symptoms such as vomiting, stomach pain, and even damage to the kidneys and/or liver, and may also cause cancers such as lung cancer and sinus cancer.
常見的六價鉻的整治手段包含物理整治法及化學整治法,其中物理整治法是藉由物理吸附的方式,避免六 價鉻的擴散。化學整治法是藉由化學還原的方式,將六價鉻還原成溶解度及毒性較小的三價鉻。然而,不論是物理整治法或化學整治法,皆有二次汙染、區域侷限及/或無法長期進行等問題。 Common hexavalent chromium remediation methods include physical remediation and chemical remediation, among which physical remediation is to avoid hexavalent chromium by physical adsorption. Chromium diffusion. The chemical remediation method reduces hexavalent chromium to trivalent chromium with less solubility and toxicity by means of chemical reduction. However, both the physical remediation method and the chemical remediation method have problems such as secondary pollution, regional limitations and/or inability to perform for a long time.
至於生物整治法則利用生物之代謝作用還原六價鉻。常見的生物整治法包含:添加微生物、營養鹽、電子供體或電子受體,以直接提高可還原六價鉻之微生物含量,或是間接藉由提供代謝作用所需反應物來促進微生物的生長及代謝。上述生物整治法也可以併用,其中添加含有營養鹽之乳化油可同時提供碳源及電子供體或電子受體,是生物整治法中經常使用的手段。然而,乳化油的油滴細小,因此容易擴散至不同種類之土壤孔隙間,並同時將營養鹽釋放,導致營養鹽快速流失,造成生物整治效果不如預期及時效性短等問題。 As for the biological remediation law, the metabolism of organisms is used to reduce hexavalent chromium. Common biological remediation methods include: adding microorganisms, nutrients, electron donors or electron acceptors to directly increase the content of microorganisms that can reduce hexavalent chromium, or indirectly to promote the growth of microorganisms by providing reactants for metabolism and metabolism. The above-mentioned biological remediation methods can also be used in combination, in which the addition of emulsified oil containing nutrient salts can simultaneously provide carbon sources and electron donors or electron acceptors, which are often used in biological remediation methods. However, the oil droplets of emulsified oil are small, so it is easy to diffuse into the pores of different types of soil, and at the same time release nutrients, resulting in rapid loss of nutrients, resulting in less than expected biological remediation effect and short timeliness.
有鑑於此,實有必要提供一種可提高生物整治六價鉻的組成物及/或方法,以解決上述問題。 In view of this, it is necessary to provide a composition and/or method that can improve the bioremediation of hexavalent chromium to solve the above problems.
因此,本發明之一樣態是提供一種現地生物整治六價鉻之凝膠組成物,其藉由添加羧甲基纖維素(carboxymethyl ether of cellulose,CMC)來調整凝膠組成物之黏度,以延緩凝膠組成物中硫酸鹽的釋放,從而促進硫酸鹽還原菌之生長及代謝,進而有效地降地汙染區之六價鉻濃度。 Therefore, one aspect of the present invention is to provide a gel composition for in-situ bioremediation of hexavalent chromium, which adjusts the viscosity of the gel composition by adding carboxymethyl ether of cellulose (CMC) to delay the The release of sulfate in the gel composition promotes the growth and metabolism of sulfate-reducing bacteria, thereby effectively reducing the concentration of hexavalent chromium in polluted areas.
本發明之另一態樣是提供一種現地生物整治六價鉻的方法,包含施予上述凝膠組成物至汙染區,以穩定釋放特定濃度的硫酸鹽,從而穩定促進硫酸鹽還原菌之生長及代謝,進而形成透水性生物反應區(permeable reactive biobarriers,PRBBs),以長期且有效地整治六價鉻。 Another aspect of the present invention is to provide a method for in-situ bioremediation of hexavalent chromium, comprising applying the gel composition to a polluted area to stably release a specific concentration of sulfate, thereby stably promoting the growth of sulfate-reducing bacteria and Metabolize, and then form permeable reactive biobarriers (PRBBs) for long-term and effective remediation of hexavalent chromium.
根據本發明之上述之態樣,提供一種現地生物整治六價鉻之凝膠組成物,其中基於凝膠組成物為1L,凝膠組成物可包含30g至50g的羧甲基纖維素(carboxymethyl ether of cellulose,CMC)、大於0.03L而不大於0.05L之乳化油,以及平衡量之硫酸鹽水溶液。上述羧甲基纖維素之黏度可例如0.3帕斯卡秒(Pa.s)至0.6Pa.s。基於上述乳化油為100重量百分比(wt%),乳化油可包含50wt%至55wt%之植物油、15wt%至20wt%界面活性劑及平衡量之水。上述硫酸鹽水溶液之濃度可例如3.0g/L至4.0g/L。 According to the above aspect of the present invention, there is provided a gel composition for on-site bioremediation of hexavalent chromium, wherein based on 1L of the gel composition, the gel composition may contain 30g to 50g of carboxymethyl cellulose (carboxymethyl ether). of cellulose, CMC), more than 0.03L but not more than 0.05L of emulsified oil, and a balanced amount of sulfate aqueous solution. The viscosity of the above-mentioned carboxymethyl cellulose can be, for example, 0.3 Pa.s (Pa.s) to 0.6Pa. s. Based on 100 weight percent (wt %) of the above emulsified oil, the emulsified oil may contain 50 to 55 wt % of vegetable oil, 15 to 20 wt % of surfactant, and a balance of water. The concentration of the above sulfate aqueous solution may be, for example, 3.0 g/L to 4.0 g/L.
依據本發明之一實施例,羧甲基纖維素之葡萄糖聚合度可例如100至2000。 According to an embodiment of the present invention, the glucose polymerization degree of carboxymethyl cellulose may be, for example, 100 to 2000.
依據本發明之一實施例,硫酸鹽水溶液之濃度可例如3.0g/L。 According to an embodiment of the present invention, the concentration of the aqueous sulfate solution may be, for example, 3.0 g/L.
依據本發明之一實施例,硫酸鹽可包含鹼金屬鹽類及/或鹼土金屬鹽類。 According to an embodiment of the present invention, the sulfate may include alkali metal salts and/or alkaline earth metal salts.
依據本發明之一實施例,乳化油可進一步包含0.001wt%至0.002wt%之複合維生素。 According to an embodiment of the present invention, the emulsified oil may further comprise 0.001wt% to 0.002wt% of multivitamins.
依據本發明之一實施例,乳化油可進一步包含0.4wt%至0.5wt%之乳酸鹽。 According to an embodiment of the present invention, the emulsified oil may further comprise 0.4 wt % to 0.5 wt % of lactate.
根據本發明之上述之態樣,提供一種現地生物整治六價鉻的方法,可包含施予凝膠組成物至汙染區,使凝膠組成物持續釋出硫酸鹽達一期間,從而促使硫酸鹽還原菌生長並分解六價鉻汙染物,其中凝膠組成物可例如上述凝膠組成物,且汙染區包含六價鉻汙染物及硫酸鹽還原菌。 According to the above aspects of the present invention, there is provided a method for in-situ bioremediation of hexavalent chromium, which may include applying a gel composition to a contaminated area, so that the gel composition continuously releases sulfate for a period of time, thereby promoting sulfate The reducing bacteria grow and decompose the hexavalent chromium pollutants, wherein the gel composition can be, for example, the above-mentioned gel composition, and the contaminated area contains the hexavalent chromium pollutants and the sulfate reducing bacteria.
依據本發明之一實施例,凝膠組成物持續釋放至少100mg/L的硫酸鹽,且期間可例如至少30天。 According to an embodiment of the present invention, the gel composition continuously releases at least 100 mg/L of sulfate, and the period may be, for example, at least 30 days.
依據本發明之一實施例,凝膠組成物持續釋放200mg/L至400mg/L的硫酸鹽,且期間可例如不小於20天。 According to an embodiment of the present invention, the gel composition continuously releases 200 mg/L to 400 mg/L of sulfate, and the period may be, for example, not less than 20 days.
應用本發明之現地生物整治六價鉻之凝膠組成物及其方法,其藉由添加羧甲基纖維素來提高黏度,藉以控制釋出的硫酸鹽濃度,從而穩定促進原生硫酸鹽還原菌之生長,進而可持續且有效地進行六價鉻的生物整治。 Applying the gel composition of the present invention for bioremediation of hexavalent chromium and the method thereof, the viscosity is increased by adding carboxymethyl cellulose, so as to control the concentration of released sulfate, thereby stably promoting the growth of native sulfate-reducing bacteria , and then sustainable and effective bioremediation of hexavalent chromium.
101,103,105,107,109,111,201,203,205,207,209,211,501,503,505,601,603,605,701,703,705,801,803,805,901,903,905,1001,1003,1005:折線 101,103,105,107,109,111,201,203,205,207,209,211,501,503,505,601,603,605,701,703,705,801,803,805,901,903,905,1001,1003,1005: Folding line
301,303,305,1101,1103,1105,1201,1203,1205:直條 301, 303, 305, 1101, 1103, 1105, 1201, 1203, 1205: Straight
400:裝置 400: Device
410:進料槽 410: Feed chute
420:蠕動泵 420: Peristaltic Pump
430:第一管柱 430: First String
440:第二管柱 440: Second String
450:第三管柱 450: Third column
432,442,452:取樣點 432,442,452: Sampling points
445:注入口 445: Injection port
460:出水槽 460: outlet tank
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之詳細說明如下:[圖1]是關於本發明之一實施例所述之不同製備例之時間對六價鉻濃度之折線圖。 In order to make the above-mentioned and other objects, features, advantages and embodiments of the present invention more obvious and easy to understand, the detailed description of the accompanying drawings is as follows: [Fig. 1] is related to different preparation examples described in one embodiment of the present invention. Line graph of time versus hexavalent chromium concentration.
[圖2]是關於本發明之一實施例所述之不同製備例中硫化物濃度對時間之折線圖。 [ Fig. 2 ] is a line graph of sulfide concentration versus time in different preparation examples described in one embodiment of the present invention.
[圖3]是關於本發明之一實施例所述之不同製備例之時間對亞硫酸還原酶(dsr A)基因含量之直條圖。 [ Fig. 3 ] is a bar graph of time versus sulfite reductase (dsr A) gene content for different preparations described in one embodiment of the present invention.
[圖4]是關於本發明之一實施例所述之管柱試驗之裝置之示意圖。 [FIG. 4] is a schematic diagram of an apparatus for a pipe string test according to an embodiment of the present invention.
[圖5]是關於本發明之一實施例所述之比較例1之時間對六價鉻濃度之折線圖。 [ Fig. 5 ] is a line graph of time versus hexavalent chromium concentration in Comparative Example 1 according to an embodiment of the present invention.
[圖6]是關於本發明之一實施例所述之比較例1之時間對硫酸鹽濃度之折線圖。 [ Fig. 6 ] is a line graph of time versus sulfate concentration for Comparative Example 1 described in one embodiment of the present invention.
[圖7]是關於本發明之一實施例所述之比較例2之時間對六價鉻濃度之折線圖。 [ Fig. 7 ] is a line graph of time versus hexavalent chromium concentration for Comparative Example 2 described in one embodiment of the present invention.
[圖8]是關於本發明之一實施例所述之比較例2之時間對硫酸鹽濃度之折線圖。 FIG. 8 is a line graph of time versus sulfate concentration for Comparative Example 2 described in one embodiment of the present invention.
[圖9]是關於本發明之一實施例所述之實施例1之時間對六價鉻濃度之折線圖。 [ Fig. 9 ] is a line graph of time versus hexavalent chromium concentration in Example 1 according to an example of the present invention.
[圖10]是關於本發明之一實施例所述之實施例1之時間對硫酸鹽濃度之折線圖。 [ Fig. 10 ] is a line graph of time versus sulfate concentration in Example 1 according to an example of the present invention.
[圖11]是關於本發明之一實施例所述之不同基質在不同時間點之drsA基因含量的直條圖。 [ Fig. 11 ] is a bar graph of the content of drsA gene at different time points in different substrates according to an embodiment of the present invention.
[圖12]是關於本發明之一實施例所述之不同基質在不同時間點之16S rRNA基因含量的直條圖。 [ Fig. 12 ] is a bar graph of the 16S rRNA gene content at different time points in different substrates according to an example of the present invention.
發明所提到的單數形式“一”、“一個”和“所述”包括複數引用,除非上下文另有明確規定。數值範圍(如
10%~11%的A)若無特定說明皆包含上、下限值(即10%≦A≦11%);數值範圍若未界定下限值(如低於0.2%的B,或0.2%以下的B),則皆指其下限值可能為0(即0%≦B≦0.2%)。上述用語是用以說明及理解本發明,而非用以限制本發明。
References herein to the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. range of values (e.g.
A) of 10%~11% includes the upper and lower limit values unless otherwise specified (ie 10%≦A≦11%); if the value range does not define the lower limit (such as B lower than 0.2%, or 0.2% The following B) means that the lower limit may be 0 (
本發明提供一種現地生物整治六價鉻之凝膠組成物,其中凝膠組成物包含硫酸鹽及羧甲基纖維素(carboxymethyl ether of cellulose,CMC),以穩定釋出硫酸鹽給土壤中的原生硫酸鹽還原菌,從而形成透水性生物反應區(permeable reactive biobarriers,PRBBs),進而長期且有效地整治六價鉻。 The present invention provides a gel composition for on-site biological remediation of hexavalent chromium, wherein the gel composition comprises sulfate and carboxymethyl ether of cellulose (CMC), so as to stably release sulfate to native natives in the soil. Sulfate-reducing bacteria, thereby forming permeable reactive biobarriers (PRBBs), and then long-term and effective remediation of hexavalent chromium.
所述「現地」(in situ)是相對於「離地」(ex situ),其中「現地」是在汙染場址現場直接處理汙染物,以避免汙染物擴散,而「離地」是將汙染物或受汙染的土壤、地下水挖出或取出,再移至他處或地面上進行處理。本發明是屬於前者,相對於後者,前者可避免汙染物的移動、環境改變、廢棄物及/或廢水排放等問題。在一些實施例中,土壤的質地並無特別限制,可例如但不限於黏土、砂質黏土、坋質黏土、砂質黏壤土、黏質壤土、坋質黏壤土、砂質壤土、壤土、坋質壤土、坋土、壤質砂土和砂土等。 The term "in situ" is relative to "ex situ", where "in situ" refers to the direct treatment of pollutants on-site at the contaminated site to avoid the spread of pollutants, and "ex situ" refers to the removal of contaminants. excavate or take out contaminated soil or groundwater, and then move it to another place or on the ground for disposal. The present invention belongs to the former, and relative to the latter, the former can avoid problems such as the movement of pollutants, environmental changes, waste and/or waste water discharge and the like. In some embodiments, the texture of the soil is not particularly limited, and can be, for example, but not limited to clay, sandy clay, loamy clay, sandy clay loam, clay loam, loamy clay, sandy loam, loam, loamy soil, loamy soil, loamy sandy soil and sandy soil, etc.
所述「六價鉻」是氧化數為+6的鉻及其化合物,可例如:三氧化鉻、鉻酸及其鹽類、重鉻酸及其鹽類。 The "hexavalent chromium" is chromium with an oxidation number of +6 and its compounds, such as chromium trioxide, chromic acid and its salts, dichromic acid and its salts.
所述「整治」是指降低土壤或地下水中的六價鉻含量,整治的方法可包含吸附六價鉻及/或將六價鉻還原成毒 性較小且較不溶於水的三價鉻。所述「生物整治」是利用微生物的代謝作用來整治六價鉻,其中微生物可例如選自原生(indigenous)微生物,因為可適應高濃度六價鉻環境而生存的微生物通常對對六價鉻具有耐受力,例如:鉻酸鹽還原菌(chromium reducing bacteria,CRB)。鉻酸鹽還原菌是可將六價鉻還原成三價鉻的細菌之統稱,且鉻酸鹽還原用以還原六價鉻的酵素稱為鉻酸鹽還原酶(chromate reductases)(如:氫化酶和細胞色素c3)。 The "remediation" refers to reducing the content of hexavalent chromium in soil or groundwater, and the remediation method may include adsorption of hexavalent chromium and/or reduction of hexavalent chromium to toxic substances. Less volatile and less water-insoluble trivalent chromium. The "biological remediation" is to use the metabolism of microorganisms to remediate hexavalent chromium, wherein the microorganisms can be selected from, for example, indigenous microorganisms, because microorganisms that can survive in a high-concentration hexavalent chromium environment are usually resistant to hexavalent chromium. Tolerance, eg: chromate reducing bacteria (CRB). Chromate reducing bacteria is a general term for bacteria that can reduce hexavalent chromium to trivalent chromium, and the enzymes used for chromate reduction to reduce hexavalent chromium are called chromate reductases (such as hydrogenases) and cytochrome c3).
部分的鉻酸鹽還原菌也是硫酸鹽還原菌(sulfate reducing bacteria,SRB)。硫酸鹽還原菌是以硫酸鹽做為呼吸作用之電子傳遞鏈的最終電子受體,其中硫酸鹽會在接受電子後形成硫化物。由於硫化物是一種強還原劑,因此硫酸鹽還原菌可間接透過硫化物來還原六價鉻。另一方面,部分硫酸鹽還原菌具有氫化酶和細胞色素c3,可直接還原六價鉻。 Some chromate-reducing bacteria are also sulfate-reducing bacteria (sulfate reducing bacteria, SRB). Sulfate-reducing bacteria use sulfate as the final electron acceptor in the electron transport chain of respiration, where sulfate will form sulfide after accepting electrons. Since sulfide is a strong reducing agent, sulfate-reducing bacteria can indirectly reduce hexavalent chromium through sulfide. On the other hand, some sulfate-reducing bacteria possess hydrogenase and cytochrome c3, which can directly reduce hexavalent chromium.
此外,硫酸鹽還原菌還可藉由生物吸附來減少游離的六價鉻。首先,鉻酸的結構與硫酸相似,因此鉻酸可藉由硫酸鹽還原菌之硫酸鹽運輸系統進入硫酸鹽還原菌中。其次,鉻酸還可被硫酸鹽還原菌之細胞壁的官能基吸附。由上述可知,利用硫酸鹽還原菌是生物整治六價鉻的良好方法。 In addition, sulfate-reducing bacteria can also reduce free hexavalent chromium through biosorption. First, the structure of chromic acid is similar to that of sulfuric acid, so chromic acid can enter sulfate-reducing bacteria through the sulfate transport system of sulfate-reducing bacteria. Second, chromic acid can also be adsorbed by functional groups of the cell walls of sulfate-reducing bacteria. As can be seen from the above, the use of sulfate-reducing bacteria is a good method for biological remediation of hexavalent chromium.
在一實施例中,生物整治是在六價鉻汙染場址的中游地區施予如營養鹽及碳源等養分,從而促進原生細菌(或微生物)之生長及代謝,進而形成透水性生物反應區 (permeable reactive biobarriers,PRBBs)。當地下水流經透水性生物反應區時,六價鉻含量可因為硫酸鹽還原菌等原生微生物之還原作用或是吸附作用而降低。在一較佳實施例中,六價鉻濃度可降至0.5g/L以下。 In one embodiment, bioremediation is to apply nutrients such as nutrients and carbon sources in the midstream area of the hexavalent chromium-contaminated site, thereby promoting the growth and metabolism of native bacteria (or microorganisms), thereby forming a water-permeable biological reaction zone. (permeable reactive biobarriers, PRBBs). When groundwater flows through the permeable biological reaction zone, the content of hexavalent chromium can be reduced due to the reduction or adsorption of native microorganisms such as sulfate-reducing bacteria. In a preferred embodiment, the hexavalent chromium concentration can be reduced to below 0.5 g/L.
所述「凝膠組成物」可包含硫酸鹽、乳化油及增稠劑,其中硫酸鹽提供電子受體,乳化油提供碳源,而增稠劑提高凝膠組成物之黏度,有利於控制硫酸鹽及乳化油釋出之速率,以避免硫酸鹽及乳化油之快速流失。在一實施例中,基於凝膠組成物為1L,凝膠組成物包含30g至50g之增稠劑、大於0.03L而不大於0.05L之乳化油,以及平衡量之硫酸鹽水溶液,其中增稠劑之黏度可例如0.3帕斯卡秒(Pa.s)至0.6Pa.s。 The "gel composition" can include sulfate, emulsified oil and thickener, wherein sulfate provides electron acceptor, emulsified oil provides carbon source, and thickener increases the viscosity of the gel composition, which is beneficial to control sulfuric acid. The rate at which salts and emulsified oils are released to avoid rapid loss of sulfates and emulsified oils. In one embodiment, based on 1 L of the gel composition, the gel composition comprises 30 g to 50 g of thickening agent, more than 0.03 L but not more than 0.05 L of emulsified oil, and a balanced amount of aqueous sulfate solution, wherein thickening The viscosity of the agent can be, for example, 0.3 Pascal seconds (Pa.s) to 0.6Pa. s.
所述「硫酸鹽」是硫酸根與金屬離子形成之鹽類,可例如:鹼金屬硫酸鹽及/或鹼土金屬硫酸鹽。在一實施例中,硫酸鹽可例如選自於由硫酸鈉、硫酸鉀、硫酸鎂及上述任意組合所組成之族群。施予硫酸鹽至六價鉻汙染場址可促進原生硫酸鹽還原菌之生長及代謝。 The "sulfate" refers to the salts formed by sulfate radicals and metal ions, such as alkali metal sulfates and/or alkaline earth metal sulfates. In one embodiment, the sulfate can be selected from, for example, the group consisting of sodium sulfate, potassium sulfate, magnesium sulfate, and any combination thereof. Sulfate administration to hexavalent chromium-contaminated sites can promote the growth and metabolism of native sulfate-reducing bacteria.
然而,如果提供過多的硫酸鹽,硫酸鹽還原菌會過度代謝而產生過多的硫化物,從而毒害硫酸鹽還原菌,反而無法有效減少六價鉻含量。如果提供的硫酸鹽過低,則無法達到促進硫酸鹽還原菌生長及代謝之效果,更無法有效還原六價鉻。經實驗證實,釋出的硫酸鹽之濃度小於或等於100mg/L時,無法有效刺激硫酸鹽還原菌之生長及代謝,而若釋出的硫酸鹽之濃度大於或等於500mg/L, 則會導致硫酸鹽還原菌過度生長及代謝,從而形成高濃度的硫化物之逆境,進而導致原地微生物(包含硫酸鹽還原菌)之死亡,因而無法有效整治六價鉻。因此,如何維持凝膠組成物釋出的硫酸鹽濃度是生物整治六價鉻的關鍵。 However, if too much sulfate is provided, the sulfate-reducing bacteria will over-metabolize and produce too much sulfide, thereby poisoning the sulfate-reducing bacteria, but cannot effectively reduce the hexavalent chromium content. If the supplied sulfate is too low, the effect of promoting the growth and metabolism of sulfate-reducing bacteria cannot be achieved, and the hexavalent chromium cannot be effectively reduced. Experiments have confirmed that when the concentration of released sulfate is less than or equal to 100mg/L, the growth and metabolism of sulfate-reducing bacteria cannot be effectively stimulated, and if the concentration of released sulfate is greater than or equal to 500mg/L, It will lead to the excessive growth and metabolism of sulfate-reducing bacteria, resulting in the formation of a high concentration of sulfide adversity, which in turn leads to the death of in-situ microorganisms (including sulfate-reducing bacteria), and thus cannot effectively remediate hexavalent chromium. Therefore, how to maintain the sulfate concentration released from the gel composition is the key to bioremediation of hexavalent chromium.
在本發明中,是藉由調整凝膠組成物之黏度來延緩高濃度之硫酸鹽之釋出,從而穩定地釋出大於100mg/L而小於500mg/L之硫酸鹽濃度。在一實施例中,硫酸鹽水溶液之濃度可例如3.0g/L至4.0g/L。在一較佳實施例中,硫酸鹽水溶液之濃度可例如3.5g/L。在上述實施例中,需在每1L之凝膠組成物中添加黏度為0.3Pa.s至0.6Pa.s之增稠劑30g至50g,以提高凝膠組成物之黏度,進而達到有效延緩硫酸鹽釋出之效果。 In the present invention, the release of high-concentration sulfate is delayed by adjusting the viscosity of the gel composition, thereby stably releasing sulfate concentration greater than 100 mg/L but less than 500 mg/L. In one embodiment, the concentration of the aqueous sulfate solution may be, for example, 3.0 g/L to 4.0 g/L. In a preferred embodiment, the concentration of the aqueous sulfate solution may be, for example, 3.5 g/L. In the above embodiment, it is necessary to add a viscosity of 0.3Pa to each 1L of the gel composition. s to 0.6Pa. 30g to 50g of thickener for s to increase the viscosity of the gel composition, thereby achieving the effect of effectively delaying the release of sulfate.
如果凝膠組成物的增稠劑之含量過低,及/或增稠劑之黏度過低,則凝膠組成物無法有效延緩硫酸鹽的釋出。如果增稠劑之含量過高,及/或增稠劑之黏度過高,則凝膠組成物釋出的硫酸鹽濃度會過低,從而無法刺激足量的硫酸鹽還原菌的生長及代謝,還可能導致地下水的濁度上升,進而增加整治的成本。 If the content of the thickener in the gel composition is too low, and/or the viscosity of the thickener is too low, the gel composition cannot effectively delay the release of sulfate. If the content of the thickener is too high, and/or the viscosity of the thickener is too high, the sulfate concentration released from the gel composition will be too low to stimulate the growth and metabolism of a sufficient amount of sulfate-reducing bacteria, It can also lead to increased turbidity in groundwater, which in turn increases remediation costs.
在一實施例中,為了避免二次汙染,增稠劑較佳為不具毒性且生物容易分解之物質。在一實施例中,增稠劑可例如羧甲基纖維素(carboxymethyl ether of cellulose,CMC)。在一實施例中,羧甲基纖維素之葡萄糖聚合度可例如為100至2000,以達到0.3Pa.s至0.6Pa.s之黏度。 In one embodiment, in order to avoid secondary pollution, the thickener is preferably a substance that is non-toxic and easily biodegradable. In one embodiment, the thickener may be, for example, carboxymethyl ether of cellulose (CMC). In one embodiment, the glucose polymerization degree of carboxymethyl cellulose can be, for example, 100 to 2000 to reach 0.3Pa. s to 0.6Pa. s viscosity.
所述「乳化油」是水、界面活性劑及長鏈脂肪酸油脂之混合物。乳化油的油滴細小且均勻,而可擴散至不同種類之土壤孔隙間,以提供原生微生物生長所需的養分。在一實施例中,凝膠組成物可包含大於0.03L而不大於0.05L之乳化油。如果乳化油的含量過低,則凝膠組成物無法提供足夠的碳源,而無法有效促進原生微生物之生長及代謝。如果乳化油的含量過高,則會導致地下水水體混濁且色度提升,反而造成整治成本增加。在一實施例中,基於乳化油為100重量百分比(wt%),乳化油可包含50wt%至55wt%之長鏈脂肪酸油脂、15wt%至20wt%界面活性劑及平衡量之水。 The "emulsified oil" is a mixture of water, surfactant and long-chain fatty acid oil. The oil droplets of emulsified oil are small and uniform, and can diffuse into the pores of different types of soil to provide nutrients for the growth of native microorganisms. In one embodiment, the gel composition may contain more than 0.03L but not more than 0.05L of emulsified oil. If the content of emulsified oil is too low, the gel composition cannot provide sufficient carbon source, and cannot effectively promote the growth and metabolism of native microorganisms. If the content of emulsified oil is too high, it will lead to the turbidity of the groundwater body and the increase of chromaticity, which will increase the cost of remediation. In one embodiment, based on 100 weight percent (wt %) of the emulsified oil, the emulsified oil may comprise 50 to 55 wt % of long chain fatty acid oils, 15 to 20 wt % of a surfactant and a balance of water.
上述長鏈脂肪酸油脂可例如植物油,其中植物油可例如選自於由大豆油、氫化棉花籽油、固態食用酥油、橄欖油、棕櫚油、椰子油及上述任意組合所組成之族群,其中長鏈脂肪酸油脂經醱酵後可產生小分子脂肪酸(如:乙酸鹽、乳酸鹽、丙酸及丁酸),以提供如硫酸鹽還原菌等厭氧生物進行代謝作用所需的碳源及能量。 The above-mentioned long-chain fatty acid oil can be, for example, vegetable oil, wherein the vegetable oil can be selected from, for example, the group consisting of soybean oil, hydrogenated cottonseed oil, solid edible shortening, olive oil, palm oil, coconut oil and any combination of the above, wherein the long-chain fatty acid After fermentation, fats and oils can produce small-molecule fatty acids (such as acetate, lactate, propionic acid, and butyric acid) to provide carbon sources and energy for metabolism by anaerobic organisms such as sulfate-reducing bacteria.
上述界面活性劑較佳為生物可分解之界面活性劑,可例如選自於由烷基聚葡萄糖苷、聚天門冬胺酸、磷脂質、聚山梨酯、單酸甘油酯、二酸甘油脂、三酸甘油酯、油酸甘油酯、泊拉沙姆、植物萃取物及其上述任意組合所組成之族群,上述植物萃取物可例如選自於由柑橘、無患子、黃花九輪草、皂皮樹、馬栗及上述任意組合所組成之族群的萃取物。在一實施例中,界面活性劑為美國加州陽光製 造公司所製造的新波綠(Simple GreenTM)。 The above-mentioned surfactant is preferably a biodegradable surfactant, which can be selected from, for example, alkyl polyglucoside, polyaspartic acid, phospholipid, polysorbate, monoglyceride, diglyceride, The group consisting of triglycerides, oleic acid glycerides, polaxamers, plant extracts and any combination thereof, the plant extracts can be selected from, for example, citrus, sapindus, japonica, saponin , horse chestnut and any combination of the above-mentioned groups of extracts. In one embodiment, the surfactant is Simple Green (TM ) manufactured by California Sunshine Manufacturing Company.
在一實施例中,乳化油可包含但不限於0.001wt%至0.002wt%之複合維生素,以協助硫酸鹽還原菌進行代謝。 In one embodiment, the emulsified oil may contain, but is not limited to, 0.001 wt % to 0.002 wt % of multivitamins to assist the metabolism of sulfate-reducing bacteria.
在一實施例中,乳化油可包含但不限於0.4wt%至0.5wt%之乳酸鹽,以直接提供小分子脂肪酸給硫酸鹽還原菌。 In one embodiment, the emulsified oil may contain, but is not limited to, 0.4 wt % to 0.5 wt % of lactate to directly provide small-molecule fatty acids to sulfate-reducing bacteria.
施予上述凝膠組成物至汙染區,可使凝膠組成物持續釋出硫酸鹽達一期間,從而促進硫酸鹽還原菌之生長及代謝,從而形成透水性生物反應區。所述「汙染區」可包含六價鉻之汙染場址及汙染場址之地下水流域的中下游。 When the gel composition is applied to the contaminated area, the gel composition can continuously release sulfate for a period of time, thereby promoting the growth and metabolism of sulfate-reducing bacteria, thereby forming a water-permeable biological reaction area. The "contaminated area" may include hexavalent chromium contaminated sites and the middle and lower reaches of the groundwater basin of the contaminated sites.
在管柱實驗中,凝膠組成物可持續釋放至少100mg/L的硫酸鹽至少30天。此外,凝膠組成物持續釋放200mg/L至400mg/L的硫酸鹽之期間可例如至少20天。上述管柱實驗之土壤種類可例如砂質壤土。 In a column experiment, the gel composition continued to release at least 100 mg/L of sulfate for at least 30 days. Furthermore, the period during which the gel composition continues to release 200 mg/L to 400 mg/L of sulfate can be, for example, at least 20 days. The soil type used in the above-mentioned string experiment can be, for example, sandy loam.
所述「有效」是指在汙染場址以特定的停留時間施用凝膠組成物,可在較短的時間內使汙染場址現場的六價鉻濃度減少至地下水管制標準。在一實施例中,較短的時間可例如半個月內,且地下水管制標準可例如小於或等於0.5mg/L,即小於第一類地下水管制標準。所述「施用的停留時間」是指在汙染場址施予凝膠組成物後至少60PV內,即使施用凝膠組成物之後,汙染場址仍持續遭到六價鉻汙染,現地微生物所形成之透水性生物反應區仍可有效降低六價鉻。 The "effective" means that the application of the gel composition at the contaminated site with a specific residence time can reduce the concentration of hexavalent chromium at the contaminated site to the groundwater control standard in a relatively short period of time. In one embodiment, the shorter time may be, for example, within half a month, and the groundwater control standard may be, for example, less than or equal to 0.5 mg/L, that is, less than the first type of groundwater control standard. The "residence time of application" refers to at least 60 PV after the gel composition is applied to the contaminated site. Even after the gel composition is applied, the contaminated site is still contaminated by hexavalent chromium, and the hexavalent chromium is still in the contaminated site. The permeable biological reaction zone can still effectively reduce hexavalent chromium.
以下利用數個實施例以說明本發明之應用,然其並非用以限定本發明,本發明技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。 Several embodiments are used below to illustrate the application of the present invention, but they are not intended to limit the present invention. Those with ordinary knowledge in the technical field of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. retouch.
實施例一、製備乳化油 Example one, preparation of emulsified oil
本實施例及下述實例中,基於乳化油為100wt%,乳化油包含50wt%之大豆油、6.67wt%之市售生物可分解之界面活性劑[品名:新波綠(Simple GreenTM);製造商:美國加州陽光製造公司(Sunshine Makers.Inc.)]、8.33wt%之大豆卵磷脂、4.17wt%之乳酸鈉、7g至10g之複合維生素,以及平衡量之超純水。 In this embodiment and the following examples, based on 100wt% of the emulsified oil, the emulsified oil contains 50wt% of soybean oil and 6.67wt% of a commercially available biodegradable surfactant [trade name: Simple Green TM ); Manufacturer: Sunshine Makers.Inc.], 8.33wt% soybean lecithin, 4.17wt% sodium lactate, 7g to 10g multivitamins, and a balanced amount of ultrapure water.
實施例二、評估不同乳化油濃度對生物整治六價鉻之影響 Example 2. Assessing the effect of different emulsified oil concentrations on the bioremediation of hexavalent chromium
挖取台灣某處鉻汙染場址挖取土質為砂質穰土之土壤及原生細菌。將土壤以121℃、15lb/in2之條件進行滅菌處理20分鐘後,獲得滅菌土壤。以下稱未經滅菌處理的土壤為現地土壤,而稱經滅菌處理的土壤為滅菌土壤。 Digging a chromium-contaminated site in Taiwan to excavate sandy soil and native bacteria. Sterilized soil was obtained after sterilizing the soil at 121° C. and 15 lb/in 2 for 20 minutes. Hereinafter, the unsterilized soil is referred to as the in situ soil, and the sterilized soil is referred to as the sterilized soil.
配置六價鉻溶液,以模擬汙染場址之地下水,其中六價鉻溶液包含80mg/L六價鉻、緩衝物質(包含:326.4mg/L之KH2PO4、1263.8mg/L之Na2HPO4、98.6mg/L之Mg2SO4.7H2O、44.1mg/L之CaCl2.2H2O、10.7mg/L之NH4Cl)、微量金屬及平衡量之水,且微量金屬之詳細成分及含量,係參閱高志明老師的團隊在2003 年發表於《水研究》(Water Research)期刊之文章,此處一併列為參考文獻。 A hexavalent chromium solution is prepared to simulate the groundwater of the polluted site, wherein the hexavalent chromium solution contains 80mg/L hexavalent chromium, buffer substances (including: 326.4mg/L KH 2 PO 4 , 1263.8mg/L Na 2 HPO 4. 98.6mg/L of Mg 2 SO 4 . 7H 2 O, 44.1mg/L of CaCl 2 . 2H 2 O, 10.7mg/L of NH 4 Cl), trace metals and balance water, and trace metals For the detailed composition and content, please refer to the article published by Mr. Gao Zhiming's team in the journal Water Research in 2003, which is listed as a reference here.
配置前導試驗樣本,其中前導試驗樣本包含六價鉻溶液130mL及4g/L碳酸氫鈉。實驗組1至3之前導試驗樣本中還包含10g之滅菌土壤,並分別包含1wt%、3wt%及5wt%之乳化油。控制組之前導試驗樣本中還包含10g之滅菌土壤,以及500mg/L之氯化汞,以維持無菌狀態。
Prepare a pilot test sample, wherein the pilot test sample contains 130mL of hexavalent chromium solution and 4g/L sodium bicarbonate. The pilot test samples of
接著,分別在第0天、第4天、第20及第36天進行RNA萃取,以獲得前導試驗樣本中細菌RNA,再利用如序列辨識編號(SEQ ID NO.):1及2所示之引子對進行即時定量聚合酶鏈鎖反應(Real-time quantitative polymerase chain reaction,qPCR),以進行16S rRNA定量步驟。RNA萃取及qPCR為本發明所屬技術領域中具有通常知識者所熟知,在此不另贅述。此外,依照環境檢驗所所公告之編號NIEA W320.52A的方法進行六價鉻定量步驟。 Next, RNA extraction was carried out on the 0th day, the 4th day, the 20th day and the 36th day, respectively, to obtain the bacterial RNA in the pilot test sample, and then use the sequence identification number (SEQ ID NO.): 1 and 2. Primer pairs were subjected to Real-time quantitative polymerase chain reaction (qPCR) for the 16S rRNA quantification step. RNA extraction and qPCR are well known to those skilled in the art to which the present invention pertains, and will not be described in detail here. In addition, the hexavalent chromium quantification step was carried out according to the method of No. NIEA W320.52A published by the Environmental Inspection Institute.
結果顯示,實驗組1至3的16S rRNA含量隨著時間的增加而增加,其中在第20天時,實驗組1至3每公升的16S rRNA含量分別為7.72×109基因複製數(gene copies)、1.69×1011基因複製數及9.80×1011基因複製數。在第36天時,實驗組1至3的16S rRNA含量分別為每公升2.18×1011基因複製數(gene copies)、8.32×1011基因複製數及1.72×1013基因複
製數,意味著乳化油濃度越高,原生細菌之生長數量越高。
The results showed that the 16S rRNA content of
控制組的六價鉻濃度不隨時間改變,而實驗組1至3的六價鉻濃度隨著時間的增加而下降,且乳化油濃度越高,六價鉻還原的比例越高,其中在第36天時,實驗組1至3的前導試驗樣本中,六價鉻含量在分別為63.9mg/L、60.8mg/L及49.7mg/L。
The concentration of hexavalent chromium in the control group did not change with time, while the concentration of hexavalent chromium in the
上述結果顯示,乳化油的濃度越高,可提升越多原生細菌(包含鉻酸鹽還原菌)的生長,因此可還原越多的六價鉻。然而,過高濃度的乳化油會導致水體混濁而產生汙染,因此,在接下來的實施例中,乳化油的濃度為5wt%。 The above results show that the higher the concentration of emulsified oil, the more the growth of native bacteria (including chromate reducing bacteria) can be promoted, and the more hexavalent chromium can be reduced. However, too high concentration of emulsified oil will cause water turbidity and pollution. Therefore, in the following examples, the concentration of emulsified oil is 5wt%.
實施例三、評估不同硫酸鹽濃度對還原六價鉻的影響 Embodiment three, assess the influence of different sulfate concentrations on reducing hexavalent chromium
配置批次試驗樣本,其中批次試驗樣本包含六價鉻溶液130mL及4g/L碳酸氫鈉水溶液。第一空白組中之批次試驗樣本中,還包含10g之滅菌土壤、5wt%之乳化油及500mg/L之氯化汞。第二空白組的批次試驗樣本中,還包含10g之現地土壤。製備比較例1的批次試驗樣本中,還包含10g之現地土壤及5wt%之乳化油。製備例1至製備例3之批次試驗樣本中,還包含有10g之現地土壤,並分別包含100mg/mL、300mg/mL或500mg/ml的硫酸鈉。 Configure batch test samples, wherein the batch test samples include 130mL of hexavalent chromium solution and 4g/L sodium bicarbonate aqueous solution. The batch test samples in the first blank group also contained 10 g of sterilized soil, 5 wt % of emulsified oil and 500 mg/L of mercuric chloride. The batch test samples of the second blank group also contained 10 g of field soil. The batch test samples of Comparative Example 1 also included 10 g of in situ soil and 5 wt % of emulsified oil. The batch test samples from Preparation Example 1 to Preparation Example 3 also contained 10 g of in situ soil, and respectively contained 100 mg/mL, 300 mg/mL or 500 mg/ml of sodium sulfate.
在第20天、第40天、第60天及第80天分別以實施二所述之方法進行六價鉻定量步驟,並依照美國HACH公司的試劑組HACH Method 8131進行美國國 家環境保護局(Environmental Protection Agency,EPA)所公告之亞甲基藍法進行硫化物含量分析步驟。接著,進行RNA萃取及16S rRNA定量步驟,並利用SEQ ID NO.:3及4所示之引子對進行qPCR,以進行異化亞硫酸鹽還原酶基因(dsrA)定量步驟。上述dsrA是硫酸鹽還原反應中的關鍵酵素。結果是顯示於圖1、圖2及圖3。 On the 20th day, the 40th day, the 60th day and the 80th day, the hexavalent chromium quantification step was carried out according to the method described in the second implementation, and the US national test was carried out according to the reagent group HACH Method 8131 of HACH Company in the United States. The sulfide content analysis step was carried out by the methylene blue method announced by the Environmental Protection Agency (EPA). Next, RNA extraction and 16S rRNA quantification steps were performed, and qPCR was performed using the primer pair shown in SEQ ID NO.: 3 and 4 to perform the dissimilatory sulfite reductase gene (dsrA) quantification step. The above-mentioned dsrA is a key enzyme in the sulfate reduction reaction. The results are shown in FIGS. 1 , 2 and 3 .
圖1是關於本發明之一實施例所述之不同製備例之時間對六價鉻濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線101、折線103、折線105、折線107、折線109及折線111分別表示第一空白組、第二空白組、製備比較例1,及製備例1至製備例3。
1 is a line graph of time versus hexavalent chromium concentration for different preparation examples described in one embodiment of the present invention, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and
如圖1所示,第一空白組(折線101)中,原生細菌經過滅菌處理後死亡,故六價鉻濃度幾乎不隨時間的增加而改變。第二空白組(折線103)中的原生細菌沒有受到抑制,但沒有額外的營養源,故只能微幅還原六價鉻。製備比較例1(折線105)含有乳化油,可促進原生細菌的生長及代謝,從而還原六價鉻,進而降低六價鉻濃度。製備例1至製備例3(折線107、折線109及折線111)之批次試驗樣本中除了乳化油,還含有硫酸鹽,故可促進硫酸鹽還原菌的生長及代謝,從而有效降低批次試驗樣本中的六價鉻濃度,其中在第80天時,製備例2(折線109)的六價鉻濃度幾乎為零。值得注意的是,相較於製備例1(折線107),製備例3(折線111)的六價鉻濃度反而較高。
As shown in FIG. 1 , in the first blank group (broken line 101 ), the native bacteria died after being sterilized, so the concentration of hexavalent chromium hardly changed with the increase of time. The protobacteria in the second blank group (polyline 103) were not inhibited, but had no additional nutrient source, so only a slight reduction of hexavalent chromium was possible. Preparation of Comparative Example 1 (broken line 105) contains emulsified oil, which can promote the growth and metabolism of native bacteria, thereby reducing hexavalent chromium, thereby reducing the concentration of hexavalent chromium. In addition to emulsified oil, the batch test samples of Preparation Example 1 to Preparation Example 3 (
圖2是關於本發明之一實施例所述之不同製備例
中硫化物濃度對時間之折線圖,其中橫軸表示時間,縱軸表示硫化物濃度,且折線201、折線203、折線205、折線207、折線209及折線211分別表示第一空白組、第二空白組、製備比較例1,及製備例1至製備例3。如圖2所示,第一空白組(折線201)、第二空白組(折線203)及製備比較例1(折線205)中幾乎無硫化物,而製備例1至製備例3中,硫化物濃度與硫酸鹽濃度正相關。
Figure 2 is a different preparation example described in relation to one embodiment of the present invention
A line graph of sulfide concentration versus time, in which the horizontal axis represents time, the vertical axis represents sulfide concentration, and
圖3是關於本發明之一實施例所述之不同製備例之時間對dsr A基因含量之直條圖,其中橫軸表示濃度,由左至右分別為對照組(即上述第二空白組)、0mg/mL(製備比較1)、100mg/mL(製備例1)、300mg/mL(製備例2)及500mg/ml(製備例3),縱軸表示dsr A基因含量,且直條301、直條303及直條305分別代表第0天、第20天及第60天。如圖3所示,相較於第0天(直條301),在第20天時(直條303),dsr A基因含量皆有上升,且上升幅度與硫酸鹽濃度正相關。但到第60天(直條305),製備例1至製備例3之dsr A基因含量不增反降,其中製備例2之dsr A基因含量高於製備例3之dsr A基因含量。
Fig. 3 is a bar graph of time versus dsr A gene content for different preparations according to an embodiment of the present invention, wherein the horizontal axis represents the concentration, and from left to right are the control group (ie, the second blank group above) , 0 mg/mL (preparation comparison 1), 100 mg/mL (preparation example 1), 300 mg/mL (preparation example 2) and 500 mg/ml (preparation example 3), the vertical axis represents the dsr A gene content, and the
綜合上述結果,可以推論越高的硫酸鹽濃度,越能促進硫酸鹽還原菌代謝,但過高的硫酸鹽濃度反而會導致過多的硫化物生成,從而抑制硫酸鹽還原菌之生長及代謝。因此,凝膠組成物釋出之硫酸鹽濃度需大於100mg/L而小於500mg/L,且300mg/L為較佳的濃度。 Based on the above results, it can be inferred that higher sulfate concentration can promote the metabolism of sulfate-reducing bacteria, but excessive sulfate concentration will lead to excessive sulfide generation, thereby inhibiting the growth and metabolism of sulfate-reducing bacteria. Therefore, the sulfate concentration released from the gel composition needs to be greater than 100 mg/L and less than 500 mg/L, and 300 mg/L is the preferred concentration.
實施例四、管柱試驗評估不同基質還原六價鉻之效率 Example 4. Evaluating the efficiency of reducing hexavalent chromium with different substrates by column test
請參閱圖4,其是關於本發明之一實施例所述之管柱試驗之裝置400之示意圖。如圖4所示,裝置400包含依序連接的進料槽(feed tank)410、蠕動泵(peristaltic pump)420、第一管柱430、第二管柱440、第三管柱450及出水槽460,其中第一管柱430、第二管柱440及第三管柱450是三支直徑5cm、長25cm之玻璃管柱,分別用以模擬汙染場址的地下水流之上游區域、中游區域及下游區域,且中第一管柱430、第二管柱440及第三管柱450分別包含取樣點432、取樣點442及取樣點452。第二管柱440上的注入口445是用來注入基質,以模擬透水性生物反應區。
Please refer to FIG. 4 , which is a schematic diagram of an
分別在第一管柱430、第二管柱440及第三管柱450中填入現地土壤,再由進料槽410提供含有80mg/L六價鉻溶液,並以蠕動泵420提供動力以進行循環浸漬,直到第一管柱430、第二管柱440及第三管柱450中的六價鉻濃度達到平衡(80mg/L),其中現地土壤之孔隙大小平均為178mL/管柱,且循環浸漬之流速為0.24L/min,故六價鉻溶液之平均停留時間為5.036小時/管柱,而總停留時間為15.11小時。考慮到取樣及換算的方便性,以2孔隙體積(Pore Volume,PV)為1天。接著,在比較例1、比較例2及實施例1中分別從注入口445注入第一基質、第二基質及第三基質,其中第一基質包含3500
mg/L之硫酸鈉、5wt%之乳化油、0.4g/mL之碳氫酸鈉及平衡量之水,第二基質包含5wt%之乳化油、40g/L之羧甲基纖維素、0.4g/mL之碳氫酸鈉及平衡量之水,且第三基質包含3500mg/L之硫酸鈉、5wt%之乳化油、40g/L之羧甲基纖維素、0.4g/mL之碳氫酸鈉及平衡量之水。
The
自取樣點432、取樣點442及取樣點452取樣,可分別獲得上游樣本、中游樣本及下游樣本,以評估在中游注入不同基質對六價鉻濃度、硫酸鹽濃度及原生細菌的影響。
From
利用如實施例二所述之方法進行六價鉻含量分析,並利用環境檢驗所編號NIEA W424.52A所公告之方法進行硫酸鹽定量步驟,再進行RNA萃取、16S rRNA定量步驟及進行16S rRNA定量步驟及dsrA定量步驟。將結果顯示於圖5至圖12中。 The content of hexavalent chromium was analyzed by the method described in Example 2, and the sulfate quantification step was carried out by the method published by the Environmental Inspection Institute No. NIEA W424.52A, followed by RNA extraction, 16S rRNA quantification, and 16S rRNA quantification. steps and dsrA quantification steps. The results are shown in FIGS. 5 to 12 .
圖5是關於本發明之一實施例所述之比較例1之時間對六價鉻濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線501、折線503及折線505分別代表比較例1之第一上游樣本、第一中游樣本及第一下游樣本。如圖5所示,第一上游樣本(折線501)之六價鉻濃度皆維持在80mg/L,第一中游樣本及第一下游樣本之六價鉻濃度在34PV(約為15天)前持續下降,但在34PV後,六價鉻濃度幾乎維持在17mg/L至19mg/L。
5 is a line graph of time versus hexavalent chromium concentration in Comparative Example 1 according to an embodiment of the present invention, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and
圖6是關於本發明之一實施例所述之比較例1之
時間對硫酸鹽濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線601、折線603及折線605分別代表比較例1之第一上游樣本、第一中游樣本及第一下游樣本。如圖6所示,第一下游樣本在每一時間點測得之硫酸鹽濃度幾乎為零,表示在注入口445注入的硫酸鹽在第二管柱440及第三管柱450中已為現地土壤中的微生物所用,或是吸附在土壤上。第一中游樣本之初始硫酸鹽濃度為1314mg/L,但在0PV至4PV時,硫酸鹽快速流失。在4PV至6PV時,硫酸鹽濃度下降幅度降低,此時所測得的硫酸鹽可能是隨著乳化油吸附於土壤顆粒上的硫酸鹽。在28PV時,硫酸鹽濃度僅剩4.39mg/L,可視為完全流失。
FIG. 6 is a diagram of Comparative Example 1 described in relation to an embodiment of the present invention.
A line graph of time versus sulfate concentration, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and the
圖7是關於本發明之一實施例所述之比較例2之時間對六價鉻濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線701、折線703及折線705分別代表比較例2之第二上游樣本、第二中游樣本及第二下游樣本。由於基質2只含有乳化油而不含硫酸鹽,相對於其他原生細菌,比較例2之硫酸鹽還原菌沒有較佳的生存優勢,因此雖然比較例2的硫酸鹽濃度最終可下降至小於0.5mg/L,但需要50PV以上的時間(如圖7之折線703及折線705所示),而不符合時間成本。
7 is a line graph of time versus hexavalent chromium concentration in Comparative Example 2 according to an embodiment of the present invention, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and
圖8是關於本發明之一實施例所述之比較例2之時間對硫酸鹽濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線801、折線803及折線805分別代
表比較例2之第二上游樣本、第二中游樣本及第二下游樣本。如圖8所示,因為第二基質不含硫酸鹽,因此第二上游樣本、第二中游樣本及第二下游樣本無硫酸鹽。
8 is a line graph of time versus sulfate concentration in Comparative Example 2 according to an embodiment of the present invention, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and
圖9是關於本發明之一實施例所述之實施例1之時間對六價鉻濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線901、折線903及折線905分別代表實施例1之第三上游樣本、第三中游樣本及第三下游樣本。如圖9所示,第三中游樣本及第三下游樣本之六價鉻濃度在0PV至22PV之間快速下降至0.9mg/L,且六價鉻濃度在32PV至60PV之間不超過0.5mg/L。
9 is a line graph of time versus hexavalent chromium concentration in Example 1 according to one embodiment of the present invention, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and
圖10是關於本發明之一實施例所述之實施例1之時間對硫酸鹽濃度之折線圖,其中橫軸表示時間,縱軸表示六價鉻濃度,且折線1001、折線1003及折線1005分別代表實施例1之第三上游樣本、第三中游樣本及第三下游樣本。由於第三基質包含羧甲基纖維素,而具有較高的黏度,因此可延緩硫酸鹽的釋出,其中在10PV至38PV時,硫酸鹽濃度是在300mg/L至500mg/L之間,且在16PV至46PV時,硫酸鹽濃度是在200mg/L至400mg/L之間。
10 is a line graph of time versus sulfate concentration in Example 1 according to one embodiment of the present invention, wherein the horizontal axis represents time, the vertical axis represents hexavalent chromium concentration, and
圖11是關於本發明之一實施例所述之不同基質在不同時間點之drsA基因含量的直條圖,其中橫軸表示組別,縱軸表示基因含量,且直條1101、直條1103及直條1105分別表示初始點(0PV)、中間點(30PV)及最後點(60PV)。如圖11所示,相較於初始點(直條1101),比
較例1、比較例2及實施例1在中間點(直條1103)的基因含量較高,但因為第二基質不含硫酸鹽而只有碳源,因此相較於比較例1及實施例1,比較例2的drsA基因含量在中間點(直條1103)時較低。此外,相較於中間點(直條1103),在最後點(直條1105)時,比較例1的drsA基因含量下降,比較例2的drsA基因含量幾乎不變,且實施例1的drsA基因含量大幅上升。
Figure 11 is a bar graph of the drsA gene content of different substrates at different time points according to an embodiment of the present invention, wherein the horizontal axis represents the group, the vertical axis represents the gene content, and the
圖12是關於本發明之一實施例所述之不同基質在不同時間點之16S rRNA基因含量的直條圖,其中橫軸表示組別,縱軸表示基因含量,且直條1201、直條1203及直條1205分別表示初始點(0PV)、中間點(30PV)及最後點(60PV)。如圖12所示,比較例2及實施例1的16S rRNA基因含量隨著時間的增加而增加,但比較例1在最後點(直條1205)之16S rRNA基因含量低於中間點(直條1203)之16S rRNA基因含量。
12 is a bar graph of the 16S rRNA gene content of different substrates at different time points according to an embodiment of the present invention, wherein the horizontal axis represents the group, the vertical axis represents the gene content, and the
由圖5至圖12之結果可以推測,第一基質因為沒有增稠劑,因此會快速釋放硫酸鹽(圖6),導致硫化物濃度過高,進而造成原生細菌(圖12直條1205)的死亡,也造成硫酸鹽還原菌整體的硫酸鹽代謝速率不增反減(圖11直條1105),故整治六價鉻的效果有限(圖5)。第二基質不含硫酸鹽而只提供碳源,雖然可以增加原生細菌的數量(圖12),但無法有效促進原生硫酸鹽還原菌代謝硫酸鹽(圖11),故使用第二基質只能緩慢還原六價鉻(圖7)。第三基質藉由添加羧甲基纖維素增加黏度,故可穩定釋出 300mg/L至500mg/L之硫酸鹽(圖10),符合實施例三所證實之較佳硫酸鹽區間(300mg/L左右),因此第三基質可穩定促進硫酸鹽還原菌之生長及代謝(圖11直條1105),從而形成透水性生物反應區,不僅可快速且有效地還原六價鉻(圖9),還可持續還原六價鉻達40PV以上(圖9,20PV至60PV)。 From the results in Figures 5 to 12, it can be speculated that the first matrix will release sulfate quickly (Figure 6) because there is no thickener (Figure 6), resulting in an excessively high concentration of sulfide, which in turn causes the protobacteria (straight bar 1205 in Figure 12). Death also caused the overall sulfate metabolism rate of sulfate-reducing bacteria to not increase but decrease (bar 1105 in Figure 11 ), so the effect of remediating hexavalent chromium was limited (Figure 5). The second matrix does not contain sulfate and only provides a carbon source. Although it can increase the number of native bacteria (Fig. 12), it cannot effectively promote the metabolism of sulfate by native sulfate-reducing bacteria (Fig. 11). Therefore, the use of the second matrix can only be slow. Reduction of hexavalent chromium (Figure 7). The viscosity of the third matrix is increased by adding carboxymethyl cellulose, so it can be released stably 300mg/L to 500mg/L of sulfate (Figure 10), in line with the preferred sulfate range (about 300mg/L) confirmed in Example 3, so the third matrix can stably promote the growth and metabolism of sulfate-reducing bacteria ( Fig. 11 bar 1105), thereby forming a water-permeable biological reaction zone, which can not only reduce hexavalent chromium rapidly and effectively (Fig. 9), but also continuously reduce hexavalent chromium above 40PV (Fig. 9, 20PV to 60PV).
由上述實施例可知,本發明之凝膠組成物,其優點在於以添加羧甲基纖維素來調整凝膠組成物之黏度,藉以控制適量的硫酸鹽釋出,從而促進原生硫酸鹽還原菌之生長,進而形成可有效還原六價鉻的透水性生物反應區。上述透水性生物反應區的效果持久,因此可減少施予凝膠組成物的頻率,並降低凝膠組成物的需求量,從而減少生物整治的成本。 As can be seen from the above examples, the gel composition of the present invention has the advantage of adjusting the viscosity of the gel composition by adding carboxymethyl cellulose, so as to control the release of an appropriate amount of sulfate, thereby promoting the growth of native sulfate-reducing bacteria. , thereby forming a water-permeable biological reaction zone that can effectively reduce hexavalent chromium. The effect of the above-mentioned water permeable bioreaction zone is long-lasting, thus reducing the frequency of applying the gel composition and reducing the required amount of the gel composition, thereby reducing the cost of bioremediation.
應理解的是,本發明雖使用特定的投予方式或特定的評估方式作為例示,說明本發明之凝膠組成物及其現地生物整治六價鉻的方法,惟本發明所屬技術領域中任何具有通常知識者可知,本發明並不限於此,在不脫離本發明之精神和範圍內,本發明亦可使用其他的投予方式或其他的評估方式進行。 It should be understood that, although the present invention uses a specific administration method or a specific evaluation method as an example to illustrate the gel composition of the present invention and the method for on-site bioremediation of hexavalent chromium, it is not intended for anyone in the technical field to which the present invention pertains. Those skilled in the art can understand that the present invention is not limited to this, and the present invention can also be carried out using other administration methods or other evaluation methods without departing from the spirit and scope of the present invention.
雖然本發明已以數個實施例揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed above with several embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention belongs, without departing from the spirit and scope of the present invention, can make various Therefore, the scope of protection of the present invention should be determined by the scope of the appended patent application.
<110> 國立中山大學 <110> National Sun Yat-Sen University
<120> 現地生物整治六價鉻之凝膠組成物及方法 <120> In situ bioremediation of hexavalent chromium gel composition and method
<140> TW 109128796 <140> TW 109128796
<141> 2020-08-24 <141> 2020-08-24
<160> 4 <160> 4
<210> 1 <210> 1
<211> 22 <211> 22
<212> DNA <212> DNA
<213> 人工序列 <213> Artificial sequences
<220> <220>
<223> 16S rRNA上游引子 <223> 16S rRNA upstream primer
<400> 1 <400> 1
<210> 2 <210> 2
<211> 16 <211> 16
<212> DNA <212> DNA
<213> 人工序列 <213> Artificial sequences
<220> <220>
<223> 16S rRNA下游引子 <223> 16S rRNA downstream primer
<400> 2 <400> 2
<210> 3 <210> 3
<211> 20 <211> 20
<212> DNA <212> DNA
<213> 人工序列 <213> Artificial sequences
<220> <220>
<223> dsrA基因上游引子 <223> dsrA gene upstream primer
<400> 3 <400> 3
<210> 4 <210> 4
<211> 20 <211> 20
<212> DNA <212> DNA
<213> 人工序列 <213> Artificial sequences
<220> <220>
<223> dsrA基因下游引子 <223> Primer downstream of dsrA gene
<400> 4 <400> 4
901, 903, 905: 直條901, 903, 905: Straight
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TW201546256A (en) * | 2014-06-03 | 2015-12-16 | Univ Nat Sun Yat Sen | Nutrimental substrate and method of in-situ remediating heavy-metal contaminated groundwater using the same |
TW202023385A (en) * | 2018-08-28 | 2020-07-01 | 美商維迪希安生命科學美國公司 | Extended and continuous release compositions for plant health and methods of use |
CN111360062A (en) * | 2018-12-26 | 2020-07-03 | 有研工程技术研究院有限公司 | Mixed microorganism for repairing polluted soil and microorganism repairing method for wet detoxification chromium residue yard polluted soil |
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TW201546256A (en) * | 2014-06-03 | 2015-12-16 | Univ Nat Sun Yat Sen | Nutrimental substrate and method of in-situ remediating heavy-metal contaminated groundwater using the same |
TW202023385A (en) * | 2018-08-28 | 2020-07-01 | 美商維迪希安生命科學美國公司 | Extended and continuous release compositions for plant health and methods of use |
CN111360062A (en) * | 2018-12-26 | 2020-07-03 | 有研工程技术研究院有限公司 | Mixed microorganism for repairing polluted soil and microorganism repairing method for wet detoxification chromium residue yard polluted soil |
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