PAHs污染土壤生物修復(fù)技術(shù)及強(qiáng)化手段研究進(jìn)展

鄭學(xué)昊, 孫麗娜, 劉克斌, 王 巖, 榮璐閣, 張 超, 陳宗聰

(沈陽大學(xué) 區(qū)域污染環(huán)境生態(tài)修復(fù)教育部重點(diǎn)實(shí)驗(yàn)室, 遼寧 沈陽 110044)

PAHs污染土壤生物修復(fù)技術(shù)及強(qiáng)化手段研究進(jìn)展

鄭學(xué)昊, 孫麗娜, 劉克斌, 王 巖, 榮璐閣, 張 超, 陳宗聰

(沈陽大學(xué) 區(qū)域污染環(huán)境生態(tài)修復(fù)教育部重點(diǎn)實(shí)驗(yàn)室, 遼寧 沈陽 110044)

綜合土壤修復(fù)的研究成果,著重介紹了PAHs土壤污染的微生物修復(fù)技術(shù)、植物修復(fù)技術(shù)和生物復(fù)合修復(fù)技術(shù).隨后總結(jié)了幾種較為通用的技術(shù)強(qiáng)化手段,包括添加表面活性劑提升PAHs生物有效性,施加調(diào)控形成共代謝機(jī)制,添加營(yíng)養(yǎng)物質(zhì)刺激土壤細(xì)菌生物活性和利用電效應(yīng)提升PAHs區(qū)域濃度,最后針對(duì)PAHs污染土壤生物技術(shù)研究的發(fā)展前景提出建議和展望.

PAHs; 污染土壤; 生物修復(fù); 強(qiáng)化方法

土壤是生命賴以生存的物質(zhì)基礎(chǔ),人類的一切生命活動(dòng)都離不開土壤[1].近年來,我國(guó)土壤污染問題日趨嚴(yán)重,周生賢指出,我國(guó)受污染的耕地約有1 000萬公頃,占全國(guó)總耕地面積的8.3%[2].隨著耕地環(huán)境質(zhì)量不斷下降,由此衍生出的作物污染問題已經(jīng)嚴(yán)重影響了食品安全及農(nóng)業(yè)經(jīng)濟(jì)發(fā)展.

1 PAHs污染現(xiàn)狀

多環(huán)芳烴(polycyclic aromatic hydrocarbons PAHs)是指由2個(gè)或2個(gè)以上的苯環(huán)以直鏈狀、角狀或串狀排列組成的有機(jī)化合物[3].PAHs本身并沒有毒性,但其進(jìn)入細(xì)胞后表現(xiàn)為三致效應(yīng)(致畸,致癌,致突變),并且隨苯環(huán)數(shù)目增加,其生物毒性也隨之增加.PAHs主要源自化石燃料不完全燃燒,含PAHs廢氣通過大氣沉降效應(yīng)使PAHs在土壤中聚集造成土壤污染,農(nóng)作物在PAHs污染土壤中生長(zhǎng)會(huì)攝取土壤中的PAHs,嚴(yán)重威脅人類健康.美國(guó)環(huán)保局(EPA)于1976年率先提出將16種PAHs列為優(yōu)先控制污染物,我國(guó)環(huán)保部1990年也將7種PAHs列入中國(guó)環(huán)境優(yōu)先控制污染物黑名單[4].由于南北方能源結(jié)構(gòu)的不同造成我國(guó)土壤中PAHs總含量跨度很大,范圍在0.83～146 689 ng/g之間,有研究者對(duì)幾個(gè)重點(diǎn)城市的PAHs污染程度進(jìn)行調(diào)查,結(jié)果表明北京、大連、天津等地區(qū)土壤中PAHs的污染水平屬于嚴(yán)重污染[5],據(jù)早年估算,我國(guó)每年P(guān)AHs排放量已經(jīng)超過25 000 t[6],而如今城市快速發(fā)展,隨著化石燃料消耗不斷升高,我國(guó)面臨的PAHs污染治理任務(wù)十分嚴(yán)峻.

2 生物修復(fù)技術(shù)

PAHs污染土壤修復(fù)方法除生物方法外還包括物理方法和化學(xué)方法.物理方法有客土法、翻土法,此類方法修復(fù)成本較高,需要消耗大量人力物力;化學(xué)方法需要向土壤中添加化學(xué)氧化劑或化學(xué)還原劑,這會(huì)破壞土壤的理化性質(zhì)繼而影響土壤微生物種群數(shù)量,產(chǎn)生二次污染.進(jìn)入到21世紀(jì),生物修復(fù)方法得到越來越多科研工作者的認(rèn)可[7],此方法成本低,專一性強(qiáng),而且環(huán)境生態(tài)風(fēng)險(xiǎn)低,如今PAHs污染土壤的生物修復(fù)技術(shù)研究在世界范圍內(nèi)已經(jīng)成為一個(gè)熱門領(lǐng)域,因此本文將著重介紹這一修復(fù)方法.

2.1微生物修復(fù)

(1) PAHs降解菌種.能對(duì)PAHs進(jìn)行降解的微生物種群分布廣泛,細(xì)菌及真菌中都存在可以降解PAHs的菌種,但不同菌種對(duì)PAHs的降解效果差異性很大,這是微生物對(duì)PAHs的特異性決定的.一般情況下,在微生物群落里,只有1%的菌種可以降解烴類化合物,但在污染環(huán)境中,這一比例可達(dá)10%[8-9],所以在污染土壤中進(jìn)行微生物提取并進(jìn)行富集馴化培養(yǎng)可以獲得PAHs專性降解菌.目前有報(bào)道的降解菌大約有200多種[10],其中細(xì)菌主要有假單胞菌[11]、芽孢桿菌[12]、黃桿菌[13]、氣單胞菌、拜葉林克氏菌、諾卡氏菌、紅球菌、分枝桿菌[14]、鞘氨醇單胞菌等[15]真菌主要包括傘蓋亞門、盤君亞門、毛霉菌亞門[16]、球囊菌門[17]、子囊菌門等.

(2) 微生物對(duì)PAHs的降解機(jī)理.無論是真菌還是細(xì)菌,在好養(yǎng)條件下降解PAHs的第一步都是加氧反應(yīng),參與此過程的酶為加氧酶,加氧酶分為兩種,包括單加氧酶和雙加氧酶[18],雙加氧酶又分為環(huán)羥基化雙加氧酶和環(huán)斷裂化雙加氧酶,其可以把兩個(gè)氧原子添加到PAHs的苯環(huán)上形成雙氧乙烷,再進(jìn)一步氧化成為順式雙氫乙醇,繼續(xù)氧化成為原兒茶酸和龍膽酸等產(chǎn)物;真菌一般產(chǎn)生單加氧酶,這種酶可對(duì)底物加1個(gè)氧原子形成芳烴化合物,再繼續(xù)被氧化成為反式雙氫乙醇和酚類[19].在厭氧條件下,國(guó)內(nèi)外相關(guān)研究較少,低環(huán)數(shù)PAHs的厭氧降解需要不同的輔酶作用逐漸開環(huán),對(duì)于高環(huán)數(shù)、高毒性的PAHs降解無論是篩選菌株還是降解機(jī)理都知之甚少[20].

(3) 土壤酶活性研究.有研究使用土壤酶來間接指示PAHs降解效率,其原因在于土壤酶主要來自于微生物的胞外分泌物,土壤酶可以展現(xiàn)土壤微生物活性及化學(xué)反應(yīng)程度[21],在某真菌實(shí)際修復(fù)PAHs過程中,PAHs去除率和轉(zhuǎn)化酶、過氧化氫酶都存在一定關(guān)聯(lián)[22],王洪等在生物修復(fù)PAHs的實(shí)驗(yàn)中發(fā)現(xiàn),PAHs去除率與脫氫酶,多酚氧化酶存在顯著的相關(guān)性,并認(rèn)為這些酶可以作為指示PAHs去除效果的微生態(tài)指標(biāo)[23].相反,PAHs濃度也會(huì)對(duì)酶活性產(chǎn)生一定影響,朱凡[24]的研究認(rèn)為,多酚氧化酶和磷酸酶對(duì)土壤質(zhì)量反應(yīng)敏感,易被土壤中PAHs激活.污染土壤修復(fù)是一個(gè)長(zhǎng)期復(fù)雜的生態(tài)過程[25],雖然酶活性變化與PAHs去除率存在一定的相關(guān)性,但是土壤酶并不能作為降解原理的唯一因素[26].

2.2植物修復(fù)

(1) 植物修復(fù)應(yīng)用現(xiàn)狀.在植物修復(fù)方法去除有機(jī)污染物的研究中,值得應(yīng)用的植物普遍具備葉片較大,根系豐富等特點(diǎn),報(bào)道較多的植物包括黑麥草,苜蓿草等[27].目前植物去除土壤PAHs方法已經(jīng)較為成熟,美國(guó)等發(fā)達(dá)國(guó)家已有利用植物大面積修復(fù)PAHs污染場(chǎng)地的實(shí)例且修復(fù)成本相當(dāng)廉價(jià),種植管理費(fèi)用每年每立方米只有0.02～1.00美元[28],同時(shí)植物也可以改善土壤周圍環(huán)境[29],應(yīng)用前景十分廣泛.在我國(guó)使用植物方法修復(fù)PAHs污染的研究中,大量實(shí)例證明,植物間種套作可以有效提高土壤中PAHs的去除效率,王嬌嬌等通過盆栽實(shí)驗(yàn)將黑麥草、蘇丹草、香根草分別與甜菜進(jìn)行間作,最優(yōu)組合對(duì)土壤中PAHs去除率可達(dá)到80%[30],張晶等將小麥、蠶豆、黑麥草三種植物分別進(jìn)行套作與單作,對(duì)比發(fā)現(xiàn)最高植物法去除PAHs效率可達(dá)64.84%,并發(fā)現(xiàn)多種植物間作更有利于PAHs去除,實(shí)驗(yàn)還對(duì)土壤中微生物數(shù)量進(jìn)行調(diào)查,結(jié)果表明套作組合土壤中的微生物數(shù)量顯著高于單作組合中土壤微生物數(shù)量[31],有學(xué)者認(rèn)為[32]此種結(jié)果與根系環(huán)境的優(yōu)化有關(guān).

(2) 植物降解機(jī)理.植物在PAHs污染土壤中生長(zhǎng)會(huì)直接吸收土壤中的PAHs,有研究者對(duì)比了植物地下部分和地上部分的PAHs含量發(fā)現(xiàn)植物體內(nèi)地下部分的含量要顯著高于地上部分[33].污染物進(jìn)入植物根系后將會(huì)被植物的木質(zhì)化作用儲(chǔ)存在植物組織中,之后將其降解為低毒性的中間產(chǎn)物或直接完全氧化降解,也存在少部分PAHs被運(yùn)輸至植物葉片,再利用蒸騰作用將其揮發(fā)至空氣中.有研究指出[34],植物雖然對(duì)PAHs有一定的積累效應(yīng),但是其修復(fù)PAHs污染土壤的主要機(jī)制并不在于此,降解PAHs的直接作用生物是根際菌群[35],植物根系分泌的酶促進(jìn)了土壤微生物生長(zhǎng),反之微生物數(shù)量的增多也會(huì)促使植物根系發(fā)育,這種植物-微生物共生關(guān)系加速土壤PAHs的去除效果.在多環(huán)芳烴對(duì)植物脅迫作用的研究中,有學(xué)者猜測(cè)PAHs[36]存在類植物生長(zhǎng)激素的作用,許多研究也得出了低濃度PAHs可以促進(jìn)植物生長(zhǎng)的類似的結(jié)論但機(jī)理尚不明確[37-38].

2.3生物復(fù)合修復(fù)

復(fù)合修復(fù)是運(yùn)用生物之間的協(xié)同作用達(dá)到快速降解土壤中PAHs的目的.兩種細(xì)菌之間會(huì)形成協(xié)同作用[39],真菌與細(xì)菌之間存在類似關(guān)系,真菌首先將污染土壤中的高環(huán)PAHs氧化為極性大、水溶性強(qiáng)、生物可利用性高的化合物,隨后細(xì)菌進(jìn)一步將該化合物完全礦化[40].

植物-微生物聯(lián)合降解PAHs方法具有修復(fù)效率較高、綠色美觀和邊修復(fù)邊生產(chǎn)等優(yōu)勢(shì).有研究表明,黑麥草、苜蓿與微生物菌劑聯(lián)合修復(fù)PAHs污染土壤比單獨(dú)的使用植物或菌劑進(jìn)行修復(fù)的效果高出1倍左右.植物的根系分泌物可以影響細(xì)菌菌群數(shù)量達(dá)到提高PAHs降解效果的目的[41],同時(shí)植物根系為微生物提供附著、生長(zhǎng)和繁殖場(chǎng)所,復(fù)合修復(fù)是一種提高PAHs降解效率的有效方法,本課題組近年來也將高效降解菌-油菜組合應(yīng)用到農(nóng)田老化PAHs污染修復(fù)研究中得到了良好的修復(fù)效果.

3 強(qiáng)化手段

3.1表面活性劑

在污染土壤中由于受到污染時(shí)間較長(zhǎng),PAHs與土壤有機(jī)質(zhì)形成了很強(qiáng)的吸附力,呈現(xiàn)為土壤有機(jī)質(zhì)膠體,生物有效性很低,表面活性劑的主要作用機(jī)理是對(duì)土壤吸附的PAHs進(jìn)行解離,使之易于被生物利用以加速PAHs去除過程,同時(shí)一些表面活性劑也可以促進(jìn)降解菌的細(xì)胞膜活性,提高降解酶活性和增強(qiáng)降解菌的基因表達(dá),過多使用表面活性劑對(duì)細(xì)胞也有一定的毒害作用,例如表面活性劑成為優(yōu)先利用底物或刺激降解菌細(xì)胞破裂等.目前在去除土壤PAHs污染的研究中,表面活性劑通常作為一種重要的強(qiáng)化措施運(yùn)用于實(shí)驗(yàn)中,在劉魏魏、尹睿[42]的研究中,添加鼠李糖脂和高效降解菌的組合比單獨(dú)添加高效降解菌的組合具有更高的降解效率,鼠李糖脂的主要作用是對(duì)PAHs的增溶,其并沒有促進(jìn)土壤中酶活性的升高,不同種表面活性劑的作用不盡相同,但無論如何,表面活性劑增效修復(fù)是最具應(yīng)用潛力的有機(jī)污染土壤修復(fù)技術(shù)之一[43].

應(yīng)用于去除PAHs的表面活性劑包括化學(xué)表面活性劑(吐溫60,吐溫80,十二烷基硫酸鈉,十二烷基苯磺酸鈉[44-46]等)和生物表面活性劑(鼠李糖脂、烷基糖苷、皂苷、海藻糖脂[47]等),目前二者都有廣泛應(yīng)用,化學(xué)表面活性劑處理成本較高且如不注意用量可能加速植物富集PAHs[48]而生物表面活化劑主要由微生物自身產(chǎn)生,降低處理成本且不會(huì)造成二次污染[49],在諸多學(xué)者的表面活性劑對(duì)比試驗(yàn)中,吐溫80、鼠李糖脂等表面活性劑因其價(jià)格低廉、可生物降解等特點(diǎn)受到研究者們的廣泛認(rèn)可[50-51].

3.2共代謝作用

共代謝是指某些有機(jī)物在環(huán)境中不能作為微生物生長(zhǎng)繁殖的唯一碳源,必須有另外的化合物存在作為微生物碳源時(shí)該有機(jī)物才能被降解的現(xiàn)象[52].這種強(qiáng)化手段主要應(yīng)用于去除高環(huán)PAHs的實(shí)驗(yàn)中,劉世亮的研究指出,苯并[a]芘作為一種高環(huán)數(shù)劇毒污染物在進(jìn)入環(huán)境中不能立刻被微生物利用,在向土壤中添加水楊酸、鄰苯二甲酸、琥珀酸鈉之后,微生物提高了對(duì)苯并[a]芘的響應(yīng)[53].添加共代謝引導(dǎo)物也可能刺激微生物在底物選擇范圍和酶分泌方面作出改變,有研究將苯二酚添加到底物中發(fā)現(xiàn)微生物的能源結(jié)構(gòu)發(fā)生了變化,從而使高環(huán)PAHs易于被微生物利用[54],有研究者將菇渣作為共代謝物質(zhì)有效刺激了白腐真菌向土壤中分泌漆酶、錳過氧化物酶等氧化酶,這些氧化酶同時(shí)也可以氧化PAHs.

3.3營(yíng)養(yǎng)物質(zhì)

根據(jù)PAHs的降解機(jī)理,PAHs降解的重要過程之一就是加氧酶催化苯環(huán)加氧開環(huán)的過程,在環(huán)境中添加適量溶解氧可以促進(jìn)PAHs的降解,20世紀(jì)就有研究者以O(shè)2、O3和H2O2作為氧源來促進(jìn)生物對(duì)PAHs的代謝[55].某種降解菌在溶解氧高于70%的條件下對(duì)PAHs的礦化率呈指數(shù)型增長(zhǎng),而溶解氧低于40%時(shí)對(duì)PAHs的礦化受到抑制[56].Sims認(rèn)為[57]土壤中無機(jī)鹽可以影響微生物去除PAHs的效率,在蘇夢(mèng)緣的正交實(shí)驗(yàn)中,通過調(diào)控營(yíng)養(yǎng)鹽質(zhì)量比、溫度、外源微生物施加量等因素最終使PAHs去除率達(dá)到較高水平[58].在鄒德勛的實(shí)驗(yàn)中,添加葡萄糖和淀粉混合物的處理提高了苯并[a]芘在土壤中的礦化速度[59],也有研究人員直接向待修復(fù)土壤中添加血粉作為營(yíng)養(yǎng)物質(zhì),強(qiáng)化土著微生物對(duì)PAHs的降解,收到良好效果.

3.4電極強(qiáng)化技術(shù)

電動(dòng)強(qiáng)化技術(shù)對(duì)于強(qiáng)化微生物降解效率是一種新技術(shù),對(duì)于有機(jī)污染物,電動(dòng)強(qiáng)化技術(shù)主要表現(xiàn)于利用電效應(yīng),將目標(biāo)反應(yīng)物輸送至污染區(qū)或生物活性區(qū),通過調(diào)節(jié)降解菌濃度,pH值,電子受體,溫度,營(yíng)養(yǎng)物以此強(qiáng)化有機(jī)污染物的降解[60-62].但由于有機(jī)物在空隙水中低溶解性的原因,增大有機(jī)物在土壤空隙水的溶解性成為提高效率的關(guān)鍵所在.

改變電壓在合理區(qū)間內(nèi)可以使微生物降解效率提高,在張燦燦、郭書海[63]的研究中,電動(dòng)-微生物修復(fù)組較無電動(dòng)強(qiáng)化修復(fù)組的降解效率有較大提高,但也有研究發(fā)現(xiàn)過高電壓會(huì)對(duì)降解過程起逆反作用,在魏巍的PAHs降解菌在電動(dòng)修復(fù)過程生物量和組成結(jié)構(gòu)變化的實(shí)驗(yàn)中發(fā)現(xiàn)過高電壓會(huì)對(duì)土壤中微生物有抑制效應(yīng)甚至致死微生物.如不對(duì)固定容器內(nèi)土壤施加合理電壓還可能在電極附近會(huì)造成極性Ph現(xiàn)象,并且隨著H2O電解產(chǎn)生H+和OH-,土壤水分也隨之降低,從而改變土壤的理化性質(zhì).

4 展 望

(1) 目前已經(jīng)發(fā)現(xiàn)了足夠多的生物物種對(duì)PAHs具有降解作用,且PAHs降解能力物種的篩選方法也已日漸成熟,應(yīng)該適當(dāng)?shù)膶⒐ぷ髦攸c(diǎn)放在不同生物降解PAHs的最優(yōu)條件研究和強(qiáng)化降解手段的研究上來.

(2) 高環(huán)數(shù)PAHs毒性大,長(zhǎng)期積累于土壤中難于去除,應(yīng)繼續(xù)探索高環(huán)PAHs去除方法和其降解機(jī)理的研究.

(3) PAHs污染研究的最終目的是實(shí)際應(yīng)用,實(shí)驗(yàn)室盆栽土壤中去除PAHs的研究已日漸完善,但大規(guī)模農(nóng)田實(shí)際修復(fù)的報(bào)道還很少見,應(yīng)逐步將研究重點(diǎn)轉(zhuǎn)移至農(nóng)田中PAHs污染土壤的實(shí)際修復(fù).

[ 1 ] 孫麗娜,呂良禾,張鴻齡. 滴滴涕污染土壤的生物修復(fù)技術(shù)[J]. 沈陽大學(xué)學(xué)報(bào)(自然科學(xué)版), 2016,28(6):446-451. (SUN L N,LYU L H,ZHANG H L. Bioremediation technology of DDT contaminated soil[J]. Journal of Shenyang University (Natural Science), 2016,28(6):446-451.)

[ 2 ] 徐麗萍. 撥開土壤污染迷霧[J]. 環(huán)境, 2013(8):14-16. (XU L P. Poke the soil pollution fog[J]. Environmental, 2013(8):14-16.)

[ 3 ] 高學(xué)晟,姜霞,區(qū)自清,等. 多環(huán)芳烴在土壤中的行為[J]. 應(yīng)用生態(tài)學(xué)報(bào), 2002,13(4):501-504. (GAO X S,JIANG X,QU Z Q,et al. Behaviors of polycyclic aromatic hydrocarbons (PAHs) in the soil[J]. Chinese Journal of Applied Ecology, 2002,13(4):501-504.)

[ 4 ] 鄭政偉,李開明,朱芳,等. 底泥中多環(huán)芳烴的微生物降解與原位修復(fù)技術(shù)[J]. 環(huán)境科學(xué)與技術(shù), 2010,33(6):55-59,110. (ZHENG Z W,LI K M,ZHU F,et al. Overviews of biodegradation of PAHs and in-situ remediation of PAHs-contaminated sediment[J]. Environmental Science & Technology, 2010,33(6):55-59,110.)

[ 5 ] 姜永海,韋尚正,席北斗,等. PAHs在我國(guó)土壤中的污染現(xiàn)狀及其研究進(jìn)展[J]. 生態(tài)環(huán)境學(xué)報(bào), 2009,18(3):1176-1181. (JIANG Y H,WEI S Z,XI B D,et al. Polycyclic aromatic hydrocarbons(PAHs) pollution in soil in China: recent advances andprospects[J]. Ecology and Environmental Sciences, 2009,18(3):1176-1181.)

[ 6 ] XU S S,LIU W X,TAO S. Emission of polycyclic aromatic hydrocarbons in China[J]. Environmental Science Technology, 2006,40(3):702-708.

[ 7 ] 張娟,劉燕. 植物修復(fù)多環(huán)芳烴污染土壤研究進(jìn)展[J]. 環(huán)境科學(xué)與技術(shù), 2016,39(6):110-116. (ZHANG J,LIU Y. Research of phytoremediation on contaminated soil with polycyclic aromatic hydrocarbons[J]. Environmental Science & Technology, 2016,39(6):110-116.)

[ 8 ] 劉國(guó)良,蘇幼明,顧書敏,等. 石油污染土壤生物修復(fù)研究新進(jìn)展[J]. 化學(xué)與生物工程, 2008,25(8):1-4. (LIU G L,SU Y M,GU S M,et al. Newprogress in bioremediation of petroleum-contaminated soil[J]. Chemistry & Bioengineering, 2008,25(8):1-4.)

[ 9 ] 高曉攀,杜賢元,李興春,等. 石油降解菌處理污染土壤的研究進(jìn)展[J]. 當(dāng)代化工, 2015,44(12):2914-2817. (GAO X P,DU X Y,LI X C,et al. Research progress of treating contaminated soil with oil-degrading bacteria[J]. Contemporary Chemical Industry, 2015,44(12):2914-2817.)

[10] 李峰. 表面活性劑對(duì)檸檬酸桿菌SA01和節(jié)桿菌SA02降解菲微界面行為的影響[D]. 杭州:浙江大學(xué), 2014. (LI F. Effect of surfactant on bacterial interfacial behaviors of phenanthrene biodegradation byCitrobactersp. SA01 andArthrobactersp. SA02[D]. Hangzhou: Zhejiang University, 2014.)

[11] 汪如婷,雒曉芳,田丹妮,等. 銅綠假單胞菌對(duì)萘和菲降解特性研究[J]. 中國(guó)釀造, 2005,34(10):82-85. (WANG R T,LUO Y F,TIAN D N,et al. Research on the degradation characteristics of naphthalene and phenanthrene byPseudomnasaeruginosa[J]. China Brewing, 2005,34(10):82-85.)

[12] FUCHEDZHIEVA N,KARAKASHEV D,ANGELIDAKI I. Anaerobic biodegradation of fluoranthene under methanogenic conditions in presence of surface-active compounds[J]. Journal of Hazardous Materials, 2008,153(1/2):123-127.

[13] 劉魏魏,尹睿,林先貴,等. 生物表面活性劑-微生物強(qiáng)化紫花苜蓿修復(fù)多環(huán)芳烴污染土壤[J]. 環(huán)境科學(xué), 2010,31(4):1079-1084. (LIU WW,YIN R,LIN X G,et al. Interaction of biosurfactant-microorganism to enhance phytoremediation of aged polycyclic aromatic hydrocarbons(PAHs) contaminated soils with alfalfa (MedicagosativaL.)[J]. Environmental Science, 2010,31(4):1079-1084.)

[14] 李全霞,范丙全,龔明波,等. 降解芘的分枝桿菌M11的分離鑒定和降解特性[J]. 環(huán)境科學(xué), 2008,29(3):763-768. (LI Q X,FAN B Q,GONG M B,et al. Isolation, identification of a pyrene-degrading strainMycobacteriumsp. M11 and its degrading characteristics[J]. Environmental Science, 2008,29(3):763-768.)

[15] 張杰,劉永生,孟玲,等. 多環(huán)芳烴降解菌篩選及其降解特性[J]. 應(yīng)用生態(tài)學(xué)報(bào), 2003,14(10):1783-1786. (ZHANG J,LIU Y S,MENG L,et al. Isolation and characteristics of PAHs-degrading strains[J]. Chinese Journal of Applied Ecology, 2003,14(10):1783-1786.)

[16] 吳宇澄,林先貴. 多環(huán)芳烴污染土壤真菌修復(fù)進(jìn)展[J]. 土壤學(xué)報(bào), 2013,50(6):1191-1199. (WU Y C,LIN X G. Fungal remediation of polycyclic aromatic hydrocarbons-contaminated soil: a review[J]. Acta Pedologica Sinica, 2013,50(6):1191-1199.)

[17] GAO Y Z,CHENG Z X,LING W T,et al. Arbuscular mycorrhizal fungal hyphae contribute to the uptake of polycyclic aromatic hydrocarbons by plant roots[J]. Bioresource Technology, 2010,101(18):6895-6901.

[18] 丁克強(qiáng),駱永明. 多環(huán)芳烴污染土壤的生物修復(fù)[J]. 土壤, 2001,33(4):169-178. (DING K Q,LUO Y M, Bioremediation of polycyclic aromatic hydrocarbons-contaminated soil[J]. Soils, 2001,33(4):169-178.)

[19] 范淑秀,李培軍,何娜,等. 多環(huán)芳烴污染土壤的植物修復(fù)研究進(jìn)展[J]. 農(nóng)業(yè)環(huán)境科學(xué)學(xué)報(bào), 2007,26(6):2007-2013. (FAN X S,LI P J,HE N,et al. Research of phytoremediation on contaminated soil with polycyclic aromatic hydrocarbons(PAHs)[J]. Journal of Agro-Environment Science, 2007,26(6):2007-2013.)

[20] 孫明明,滕應(yīng),駱永明. 厭氧微生物降解多環(huán)芳烴研究進(jìn)展[J].微生物學(xué)報(bào), 2012,52(8):931-939. (SUN MM,TENG Y,LUO Y M. Progresses in anaerobic biodegradation of polycyclic aromatic hydrocarbons-A review[J]. Acta Microbiologica Sinica, 2012,52(8):931-939.)

[21] 王理德,王方琳,郭春秀,等. 土壤酶學(xué)研究進(jìn)展[J]. 土壤, 2016,48(1):12-21. (WANG L D,WANG F L,GUO C X,et al. Review: progress of soil enzymology[J]. Soils, 2016,48(1):12-21.)

[22] 張志遠(yuǎn),王翠蘋,劉海濱,等. 可可毛色二孢菌對(duì)焦化廠土壤多環(huán)芳烴污染修復(fù)[J]. 環(huán)境科學(xué), 2012,33(8):2832-2839. (ZHANG Z Y,WANG C P,LIU H B,et al. Bioremediation of PAHscontaminated soil from Beijing coking plant by Lasiodiplodia theobromae[J]. Environmental Science, 2012,33(8):2832-2839.)

[23] 王洪,李海波,孫鐵珩,等. 生物修復(fù)PAHs污染土壤對(duì)酶活性的影響[J]. 生態(tài)環(huán)境學(xué)報(bào), 2011,20(4):691-695. (WANG H,LI H B,SUN T H,et al. Bioremediation of PAHs contaminated soil and its impacts on soil enzyme activity[J]. Ecology and Environmental Sciences, 2011,20(4):691-695.)

[24] 朱凡,洪湘琦,閆文德,等. PAHs污染土壤植物修復(fù)對(duì)酶活性的影響[J]. 生態(tài)學(xué)報(bào), 2014,34(3):581-588. (ZHU F,HONG X Q,YAN D W,et al. Enzymatic activity during phytormediation of polycyclic aromatic hydrocarbon impacted soil[J]. Acta Ecologica Sinica, 2014,34(3):581-588.)

[25] SONG Y F,SONG X Y,ZHANG W,et al. Issues concerned with the bioremediation of contaminated soils[J]. Environmental Science, 2004,25(2):129-133.

[26] 唐玉姝,魏朝富,顏廷梅,等. 土壤質(zhì)量生物學(xué)指標(biāo)研究進(jìn)展[J]. 土壤, 2007,39(2):157-163. (TANG Y S,WEI C F,YAN T M,et al. Biological indicator of soil quality: a review[J]. Soils, 2007,39(2):157-163.)

[27] 李思雯,李鵬,孫麗娜,等. 紫花苜蓿對(duì)DDT污染土壤的修復(fù)[J]. 沈陽大學(xué)學(xué)報(bào)(自然科學(xué)版), 2016,27(2):105-110. (LI S W,LI P,SUN L N,et al. Phytoremediation of DDT-contaminated soil byMedicagosativa[J]. Journal of Shenyang University (Natural Science), 2016,27(2):105-110.)

[28] CUNNINGHAM S D,BERTI W R,HUANGET J W. Phytoremediation of contaminated soils. Trends biotechnol[J]. Trend in Biotechnology, 1995,13(9):393-397.

[29] 王亞男,程立娟,周啟星. 植物修復(fù)石油烴污染土壤的機(jī)制[J]. 生態(tài)學(xué)雜志, 2016,35(4):1080-1088. (WANG Y N,CHENG L J,ZHOU Q X. Phytoremediation mechanisms of petroleum-contaminated soils[J]. Chinese Journal of Ecology, 2016,35(4):1080-1088.)

[30] 王姣姣,呼世斌,魏麗瓊,等. 甜菜與牧草間作對(duì)多環(huán)芳烴污染土壤的修復(fù)作用[J]. 農(nóng)業(yè)環(huán)境科學(xué)學(xué)報(bào), 2016,35(6):1090-1096. (WANG J J,HU S B,WEI L Q,et al. Phytoremediation of polycyclic aromatic hydrocarbons(PAHs)-contaminated soil by intercropped beet-grasses[J]. Journal of Agro-Environment Science, 2016,35(6):1090-1096.)

[31] 張晶,林先貴,曾軍,等. 植物混種原位修復(fù)多環(huán)芳烴污染農(nóng)田土壤[J]. 環(huán)境工程學(xué)報(bào), 2012, 6(1):341-346. (ZHANG J,LIN X G,ZENG J,et al. In-situ phytoremediation of PAHscontaminateds soils in a mixed cropping system[J]. Chinese Journal of Environmental Engineering, 2012,6(1):341-346.)

[32] 王效國(guó),呼世斌,承志文,等. 大豆龍葵單作和間作對(duì)芘污染土壤的修復(fù)[J]. 環(huán)境工程學(xué)報(bào), 2015,9(12):6128-6134. (WANG X G,HU S B,CHENG Z W,et al. Phytoremediation of pyrene contaminated soil by monoculture and intercropping ofGlycinemaxandSolanumnigrum[J]. Chinese Journal of Environmental Engineering, 2015,9(12):6128-6134.)

[33] 尹春芹,蔣新,楊興倫,等. 多環(huán)芳烴在土壤-蔬菜界面上的遷移與積累特征[J]. 環(huán)境科學(xué), 2008,29(11):3240-3245. (YIN C Q,JIANG X,YANG X L,et al. Characters of soil-vegetable transfer and accumulation of polycyclic aromatic hydrocarbons[J]. Environmental Science, 2008,29(11):3240-3245.)

[34] KHAN S,AIJUN L,ZHANG S,et al. Accumulation of polycyclic aromatic hydrocarbons and heavy metals in lettuce grown in the soils contaminated with long-term wastewater irrigation[J]. Journal of Hazardous Materials, 2008,152(2):506-515.

[35] 鄭學(xué)昊,孫麗娜,王曉旭,等. 植物-微生物聯(lián)合修復(fù)PAHs污染土壤的調(diào)控措施對(duì)比研究[J]. 生態(tài)環(huán)境學(xué)報(bào), 2017,26(2):323-327. (ZHENG X H,SUN L N,WANG X X,et al. Compared with different regulation on phytoremediation-microorganism combined remediation PAHs contaminated soil[J]. Ecology and Environmental Sciences, 2017,26(2):323-327.)

[36] 陳世軍,祝賢凌,馮秀珍,等. 多環(huán)芳烴對(duì)植物的影響[J]. 生物學(xué)通報(bào), 2010,45(2):9-11. (CHEN S J,ZHU X L,FENG X Z,et al. Effects of Polycyclic Aromatic Hydrocarbons on Plants[J]. Bulletin of Biology, 2010,45(2):9-11.)

[37] MCCANN J H,GREENBERG B M,SOLOMON K R. The effect of creosote on the growth of an axenic culture ofMyriophyllumspicatumL.[J]. Aquatic Toxicology, 2002,50:265-274.

[38] 王海翠,胡林林,李敏,等. 多環(huán)芳烴(PAHs)對(duì)油菜生長(zhǎng)的影響及其積累效應(yīng)[J]. 植物生態(tài)學(xué)報(bào), 2013,37(12):1123-1131. (WANG H C,HU LL,LI M,et al. Growth effects and accumulations of polycyclic aromatic hydrocarbons (PAHs) in rape[J]. Chinese Journal of Plants Ecology, 2013,37(12):1123-1131.)

[39] 劉虹,楊元元,劉娜,等. 兩種石油烴降解菌的鑒定及其對(duì)石油烴底物的降解[J]. 環(huán)境污染與防治, 2016,38(6):28-33. (LIU H,YANG YY,LIU N,et al. Identification of two petroleum hydrocarbons strains and the degradation of petroleum hydrocarbons substrate by the strains[J]. Environmental Pollution and Control, 2016,38(6):28-33.)

[40] 張銀萍,王芳,楊興倫,等. 土壤中高環(huán)多環(huán)芳烴微生物降解的研究進(jìn)展[J]. 微生物學(xué)通報(bào), 2010,27(2):280-288. (ZHANG Y P,WANG F,YANG X L,et al. Recentadvances in biodegradation of high-molecular weight PAHs in soil[J]. Microbiology China, 2010,27(2):280-288.)

[41] 楊靜. PAHs污染土壤植物修復(fù)的根際效應(yīng)及機(jī)制[D]. 杭州:浙江大學(xué), 2012. (YANG J. Study on the rhizosphere effects and mechanisms in phytoremediation for PAHs contaminated soils[D]. Hangzhou: Zhejiang University, 2012.)

[42] 劉魏魏,尹睿,林先貴,等. 生物表面活性劑強(qiáng)化微生物修復(fù)多環(huán)芳烴污染土壤的初探[J]. 土壤學(xué)報(bào), 2010,47(6):1118-1125. (LIU WW,YI R,LIN X G,et al. Effect of biosurfactant enhancing bioremediation of polycyclic aromatic hydrocarbons(PAHs) contaminated solis[J]. Acta Pedologica Sinica, 2010,47(6):1118-1125.)

[43] 朱利中. 有機(jī)污染物界面行為調(diào)控技術(shù)及其應(yīng)用[J]. 環(huán)境科學(xué)學(xué)報(bào), 2012,32(11):2641-2649. (ZHU L Z. Controlling technology of interfacial behaviors of organic pollutants and its application[J]. Acta Scientiae Circumstantiae, 2012,32(11):2641-2649.)

[44] BAUTISA L F,SANZ R,MOLINA M C,et al. Effect of different non-ionic surfactants on the biodegradation of PAHs by diverse aerobic bacteria[J]. International Biodeterioration & Biodegradation, 2009,63(7):913-922.

[45] CHENG M,ZENG G,HUANG D,et al. Advantages and challenges of Tween 80 surfactant-enhanced technologies for the remediation of soils contaminated with hydrophobic organic compounds[J]. Chemical Engineering Journal, 2017,314:98-113.

[46] JANG S A,LEE D S,LEE M W,et al. Toxicity of phenanthrene dissolved in nonionic surfactant solutions to Pseudomonas putida P2[J]. FEMS Microbiology Letters, 2007,26(7):194-199.

[47] KACZOREK E,SALEK K,GUZIK U,et al. Cell surface properties and fatty acids composition of Stenotrophomonas maltophilia under the influence of hydrophobic compounds and surfactants[J]. New Biotechnology, 2012,30(2):173-182.

[48] 李瀅,區(qū)自清,孫鐵珩. 表面活性劑對(duì)小麥吸收多環(huán)芳烴(PAHs)的影響[J]. 生態(tài)學(xué)報(bào), 2000,20(1):99-102. (LI Y,OU Z Q,SUN T H. Effects of surfactants on the uptake of PAH s by wheat[J]. Acta Ecologica Sinica, 2000,20(1):99-102.)

[49] 郭楚玲,鄭天凌,洪華生. 多環(huán)芳烴的微生物降解與生物修復(fù)[J]. 海洋環(huán)境科學(xué), 2000,19(3):24-29. (GUO C L,ZHENG T L,HONG H S. Biodegradation and bioremediation of polycyclic aromatic hydrocarbons[J]. Marine Environmental Science, 2000,19(3):24-29.)

[50] 李果,毛華軍,鞏宗強(qiáng),等. 幾種表面活性劑對(duì)柴油及多環(huán)芳烴的增溶作用[J]. 環(huán)境科學(xué)研究, 2011,24(7):775-780. (LI G,MAO H J,GONG Z Q,et al. Solubilization of Diesel and Polycyclic Aromatic Hydrocarbons by Certain Kinds of Surfactants[J]. Research of Environmental Sciences, 2011,24(7):775-780.)

[51] PEKDEMIR T,COPUR M,URUM K. Emulsification of crude oil-water systems using biosurfactants[J]. Process Salty and Environmental Protection, 2005,83(1):38-46.

[52] 王曉蓉. 環(huán)境化學(xué)[M]. 南京:南京大學(xué)出版社, 1997. (WANG X R. Environmental Chemistry[M]. Nanjing: Nanjing University Press, 1997.)

[53] 劉世亮,駱永明,吳龍華,等. 污染土壤中苯并[a]芘的微生物共代謝修復(fù)研究[J]. 土壤學(xué)報(bào), 2010,47(2):364-369. (LIU S L,LUO Y M,DING K Q,et al. Rhizosphere remediation and i ts mechanism of benzo[a] pyrene-contaminated Soil by Growing Ryegrass[J]. Acta Pedologica Sinica, 2007,26(2):526-532.)

[54] 黃興如,張彩文,楊瑞杰,等. 多環(huán)芳烴降解菌的篩選、鑒定及降解特性[J]. 微生物學(xué)通報(bào), 2016,43(5):965-973. (HUANG X R,ZHANG C W,YANG R J,et al. Isolation, identification and degrading properties of PAHs-degrading bacteria[J]. Microbiology China, 2016,43(5):965-973.)

[55] MORGAN P,WATKINSON R J. Factors limiting the supply and efficiency of nutrient and oxygen supplements for the in situ biotreatment of contaminated soil and groundwater[J]. Water Research, 1992,26:73-78.

[56] BOYD T J,MONTGOMERY M T,STEELE J K,et al. Dissolved oxygen saturation controls PAHs biodegradation in freshwater estuary sediments[J]. Microbial Ecology, 2005,49(2):226-235.

[57] SIMS J L,Sims R C,MATTHEWS J E. Approach to bioremediation of contaminated soil[J]. Hazardous Waste and Hazardous Materials, 1990,7(2):117-149.

[58] 蘇夢(mèng)緣,王紅旗,李藝,等. 多環(huán)芳烴降解菌菌群構(gòu)建及其適宜降解環(huán)境條件的確定[J]. 環(huán)境工程學(xué)報(bào), 2017,11(2):1192-1198. (SU M Y,WANG H Q,LI Y,et al. Construction of microbial consortia for PAHs degradation and appropriate environmental condition for degradation[J]. Chinese Journal of Environmental Engineering, 2017,11(2):1192-1198.)

[59] 鄒德勛,駱永明,滕應(yīng),等. 多環(huán)芳烴長(zhǎng)期污染土壤的微生物強(qiáng)化修復(fù)初步研究[J]. 土壤, 2006,38(5):652-656. (ZOU D X,LUO Y M,TENG Y,et al. Enhanced microbial remediation of long-term polycyclic aromatic hydrocarbons (PAHs) polluted soils[J]. Soils, 2006,38(5):652-656.)

[60] 羅啟仕,王慧,張錫輝,等. 電動(dòng)力學(xué)強(qiáng)化原位生物修復(fù)研究進(jìn)展[J]. 環(huán)境污染與防治, 2004,26(4):268-271. (LUO S Q,WANG H,ZHANG X H,et al. Enhancement of in-situ bioremediation byelectrokinetic technology[J]. Environmental Pollution and Control, 2004,26(4):268-271.)

[61] 馬建偉,王慧,羅啟仕,等. 利用電動(dòng)技術(shù)強(qiáng)化有機(jī)污染土壤原位修復(fù)研究[J]. 環(huán)境工程學(xué)報(bào), 2007,1(7):119-124. (MA J W,WANG H,LUO Q S,et al. Enhancement of in-situ remediation of organics byelectrokinetic[J]. Chinese Journal of Environmental Engineering, 2007,1(7):119-124.)

[62] 魏巍. PAHs降解菌的分離及在電廠中的降解特性研究[D]. 沈陽:沈陽大學(xué), 2014. (WEI W. Isolation of PAHs-degrading strains and their degradation capability in electric field[D]. Shenyang: Shenyang University, 2014.)

[63] 張燦燦,郭書海,李婷婷,等. 焦化廠高環(huán)PAHs污染土壤的電動(dòng)-微生物修復(fù)[J]. 環(huán)境工程, 2014,32(7):150-154. (ZHANG C C,GUO S H,LI T T,et al. Electro-bioremediation of coking plant soils contaminated with high-molecular polycyclic aromatic hydrocarbons[J]. Environmental Engineering, 2014,32(7):150-154.)

PAHsContaminatedSoilBioremediationTechnology:AReview

ZhengXuehao,SunLina,LiuKebin,WangYan,RongLuge,ZhangChao,ChenZongcong

(Key Laboratory of Regional Environment and Eco-Remediation (Ministry of Education), Shenyang University, Shenyang 110044, China)

Based on the research achievements of soil remediation in recent years, the microbial remediation technology, phytoremediation technology and bioremediation repair technology of PAHs soil pollution were introduced emphatically. Then a few common means of technical strengthening were given, including the addition of surfactants to enhance the bioavailability of PAHs, the regulation of the formation of co-metabolism mechanism, the addition of nutrients to stimulate soil biological activity and the use of electrical effects to enhance PAHs regional concentration. At last the future development prospects were put forward.

PAHs; contaminated soil; bioremediation; strengthening method

X 53

: A

【責(zé)任編輯:胡天慧】

2017-02-07

國(guó)家重點(diǎn)基礎(chǔ)研究發(fā)展計(jì)劃項(xiàng)目(2014CB441106); 沈陽市科技計(jì)劃項(xiàng)目(F14-133-9-00).

鄭學(xué)昊(1992-),男,遼寧沈陽人,沈陽大學(xué)碩士研究生; 孫麗娜(1960-),女,遼寧北票人,沈陽大學(xué)教授,博士生導(dǎo)師.

2095-5456(2017)04-0297-07