摘要:通過盆栽試驗研究了三維電場對博落回修復(fù)鈾污染土壤性能的強(qiáng)化作用。結(jié)果表明:與二維電場相比,三維電場與博落回耦合可使博落回地上和地下部分鈾質(zhì)量分?jǐn)?shù)分別提高17.14 %和43.3 %,干生物量分別提高40.4 %和37.6 %,土壤中可交換態(tài)鈾石比提高10百分點,改變了博落回體內(nèi)鈾的亞細(xì)胞分布,增加了鈾在博落回體內(nèi)的積累,促進(jìn)鈾向博落回細(xì)胞器內(nèi)轉(zhuǎn)移,其中莖部鈾的轉(zhuǎn)移更為明顯。三維電場可進(jìn)一步強(qiáng)化博落回對鈾污染土壤的修復(fù)作用,是一種具有潛在應(yīng)用前景的強(qiáng)化植物修復(fù)方法。
關(guān)鍵詞:三維電場;植物修復(fù);博落回;鈾污染;土壤;生物修復(fù)
中圖分類號:TD167"X53"""""""""文章編號:1001-1277(2024)08-0112-05
文獻(xiàn)標(biāo)志碼:Adoi:10.11792/hj20240818
引"言
天然鈾資源開采過程中會產(chǎn)生大量的鈾尾礦及含鈾溶液,其在人為或自然等因素影響下可能會進(jìn)入到土壤中,從而導(dǎo)致土壤鈾污染,對人體健康產(chǎn)生較大威脅。目前,鈾污染土壤修復(fù)方法主要有自然衰減法、物理法、化學(xué)法及生物法[1]。生物修復(fù)技術(shù)主要分為植物修復(fù)技術(shù)和微生物修復(fù)技術(shù),其中,植物修復(fù)技術(shù)可實現(xiàn)污染物的原位去除,是生物修復(fù)技術(shù)的研究熱點[2]。但是,單一植物修復(fù)技術(shù)在應(yīng)用過程中仍存在一定的問題,如修復(fù)效率較低、易受環(huán)境影響、修復(fù)周期較長等[3]。因此,植物修復(fù)技術(shù)與其他技術(shù)聯(lián)合有望解決單一植物修復(fù)技術(shù)存在的弊端[4-5]。
電動強(qiáng)化植物修復(fù)技術(shù)主要利用電場有效地將可溶性帶電污染物驅(qū)向植物根系,增加金屬的生物有效性,促進(jìn)植物對污染物的吸收與積累[6-8]。目前,電動強(qiáng)化植物修復(fù)技術(shù)的研究中,電動修復(fù)體系通常為二維電極體系,其在運行過程中具有一定的缺陷,如pH依賴性、濃差極化及二次電化學(xué)反應(yīng)等[9-10]。三維電極法是一種新型的化學(xué)處理技術(shù),通過在傳統(tǒng)電解槽兩端電極間裝填碎屑或粒狀工作電極材料,使其表面帶電形成第三極,加強(qiáng)水解和傳質(zhì),提高反應(yīng)效率[11-12]。因此,第三極材料的理化性質(zhì)對三維電極法的性能起關(guān)鍵作用[13-14]。生物質(zhì)導(dǎo)電炭具有優(yōu)良的導(dǎo)電性,可作為第三極材料用于構(gòu)建三維電場修復(fù)體系[15]。有研究表明,在植物修復(fù)過程中向土壤基質(zhì)中添加適宜濃度的生物炭材料可提高植物對重金屬的積累及轉(zhuǎn)運,促進(jìn)植物根、莖、葉的生長,同時緩解重金屬誘發(fā)的氧化脅迫損傷[16-17]。此外,在土壤中添加生物炭材料可提高土壤孔隙率、持水性能、pH、速效鉀及有機(jī)質(zhì)含量[18]。與普通導(dǎo)電炭材料相比,導(dǎo)電炭氣凝膠材料表現(xiàn)出更大的比表面積和豐富的孔結(jié)構(gòu),且可保持三維結(jié)構(gòu)[19],同時有望改善土壤條件。
本文以廢棄咖啡渣作為原料,經(jīng)凝膠化、高溫催化炭化處理制備導(dǎo)電炭氣凝膠材料,構(gòu)建三維電場修復(fù)體系,研究三維電場修復(fù)體系對博落回電動耦合體系修復(fù)鈾污染土壤性能的強(qiáng)化作用,并通過分析博落回體內(nèi)酶活性、植物根際土壤中鈾結(jié)合形態(tài)變化、鈾在植物體內(nèi)亞細(xì)胞分布,揭示三維電場強(qiáng)化博落回-電動耦合體系修復(fù)鈾污染土壤的作用機(jī)制,以期建立三維電場-植物修復(fù)耦合體系強(qiáng)化博落回修復(fù)鈾污染土壤的方法。
1"材料與方法
1.1"試驗材料
1.1.1"供試土壤
供試土壤由無污染土壤與U3O8溶液配制而成,其中無污染土壤取自南華大學(xué)校園表層土(0~20 cm)。具體配制過程如下:首先,將無污染土壤去除樹葉和大石塊后過60目篩,取篩下土壤樣品置于高壓滅菌鍋(121 ℃、101 kPa)中滅菌2 h;然后,將2.9 L 1 g/L U(Ⅵ)溶液分2次添加到滅菌后的土壤樣品中,攪拌均勻;最后,將混合均勻的土壤樣品穩(wěn)定60 d,每隔7 d攪拌一次。供試土壤中鈾質(zhì)量分?jǐn)?shù)為(29.86±0.36)mg/kg。
1.1.2"供試植物
供試博落回由種子萌發(fā)后培養(yǎng)獲得,其中博落回種子購買于衡陽市某花鳥市場。具體操作如下:首先,用1 %次氯酸鈉(NaClO)溶液對博落回種子消毒30 min;然后,用無菌水將消毒處理后的博落回種子沖洗3~5遍,并將種子在無菌水中浸泡12 h,以打破種子的休眠;隨后,將種子濾出,晾至半干后播種在已滅菌的營養(yǎng)土中,放置于溫室大棚中發(fā)芽2周;最后,選取生長8周且長勢一致的博落回進(jìn)行盆栽試驗。
1.1.3"導(dǎo)電炭氣凝膠
類腐殖質(zhì)基水凝膠制備:稱取一定量經(jīng)水煮后的咖啡渣,加入裝有3 mol/L KOH溶液的燒杯中;將燒杯置于80 ℃水浴加熱器中攪拌3 h后進(jìn)行固液分離,上清液為類腐殖質(zhì)(HLSs)溶液;將HLSs溶液與丙烯酸(AA)以體積比2∶1進(jìn)行混合,再加入交聯(lián)劑與引發(fā)劑混合均勻,置于80 ℃烘箱中2 h,進(jìn)行凝膠化處理,得到類腐殖質(zhì)基水凝膠。
2024年第8期/第45卷""安環(huán)與分析安環(huán)與分析""黃"金
導(dǎo)電炭氣凝膠制備及表征:將冷凍干燥處理后的類腐殖質(zhì)基水凝膠置于真空高溫?zé)Y(jié)爐中,分別在800 ℃、900 ℃、1 000 ℃和1 100 ℃下進(jìn)行炭化并保溫1 h,得到不同溫度條件下制備的導(dǎo)電炭氣凝膠;采用四探針測量儀(MG-6)測量導(dǎo)電炭氣凝膠的導(dǎo)電性能。
1.2"修復(fù)體系構(gòu)建
選取生長8周且長勢一致的博落回構(gòu)建博落回-電動耦合體系(U+P+AC),其中,電極材料為石墨電極,陰極與陽極的電極間距15 cm,電極插入土壤深度15 cm,電場強(qiáng)度1 V/cm,通電時間24 h/d,持續(xù)20 d。盆栽試驗在南華大學(xué)溫室大棚中進(jìn)行,共設(shè)2個試驗組,每個試驗組設(shè)3個平行樣。通過向U+P+AC中的供試土壤加入100 mg/kg導(dǎo)電炭氣凝膠,構(gòu)建博落回-三維電動耦合體系(U+P+AC+C)。
1.3"測定方法
1.3.1"博落回生物量測定
鮮生物量測定:試驗結(jié)束后,分別收集博落回地上與地下部分,用去離子水沖洗干凈,隨后置于20 mmol/L Na2EDTA溶液中浸泡30 min,去除吸附在表面的U,然后用吸水紙吸干表面水分,稱量,即為博落回地上與地下部分鮮生物量。
干生物量測定:將測定鮮生物量后的博落回地上與地下部分置于105 ℃烘箱中殺青30 min,然后將烘箱調(diào)溫至70 ℃,烘至恒質(zhì)量,冷卻后稱量,即得博落回地上與地下部分干生物量。
1.3.2"鈾含量及賦存形態(tài)測定
博落回中鈾含量測定:分別取0.2 g殺青后的博落回地上與地下部分加入HNO3-HClO4混合溶液(體積比為4∶1)中,使用石墨消解儀進(jìn)行消解,待消解完成后,用3 %稀硝酸將上清液定容至25 mL,然后用電感耦合等離子體質(zhì)譜儀(ICP-MS)測定博落回地上與地下部分中的鈾含量。
土壤中鈾賦存形態(tài)測定:采用改進(jìn)后的Tessier法[20]對土壤中鈾賦存形態(tài)進(jìn)行測定,其中鈾濃度采用ICP-MS測定。
1.3.3"博落回體內(nèi)相關(guān)酶活性
利用上海柯意哲科學(xué)實驗室生產(chǎn)的試劑盒,測定植物地上部分過氧化物酶(POD)、超氧化物歧化酶(SOD)、丙二醛(MDA)及過氧化氫酶(CAT)的含量。
1.3.4"亞細(xì)胞分布
采用差速離心法對鈾的亞細(xì)胞分布進(jìn)行測定。細(xì)胞壁和細(xì)胞器組分采用石墨消解法進(jìn)行消解,ICP-MS測定消解后的樣品及細(xì)胞可溶性樣品中的鈾含量。
2"結(jié)果與討論
2.1"導(dǎo)電炭氣凝膠表征
不同炭化溫度下制備的導(dǎo)電炭氣凝膠電阻率變化曲線見圖1。從圖1可以看出:隨著炭化溫度的升高,導(dǎo)電炭氣凝膠的電阻率先降低后上升,1 000 ℃時電阻率達(dá)最低值。當(dāng)炭化溫度低于1 000 ℃時,導(dǎo)電炭內(nèi)部的羰基和脂肪族官能團(tuán)被破壞,內(nèi)部分子結(jié)構(gòu)重排,芳構(gòu)化程度、結(jié)晶度和石墨化程度增強(qiáng),從而導(dǎo)致其電阻率隨溫度升高而降低[21-22]。當(dāng)炭化溫度高于1 000 ℃時,隨著炭化溫度繼續(xù)升高,導(dǎo)電炭中的揮發(fā)分析出減少,絡(luò)合作用變?nèi)?,且石墨化程度趨于穩(wěn)定,因此電阻率隨溫度升高略有上升。綜合考慮,選用炭化溫度為1 000 ℃的導(dǎo)電炭氣凝膠作為第三極材料。
2.2"三維電場對土壤pH的影響
不同處理組陰陽極土壤pH變化見圖2。從圖2可以看出:在為期20 d電場強(qiáng)度為1 V/cm的直流電源作用下,2個處理組中陽極與陰極土壤分別出現(xiàn)明顯的酸化與堿化,其中U+P+AC+C組陰極與陽極土壤pH的差值小于U+P+AC組。這表明三維電場可有效降低電動修復(fù)對土壤pH的影響。事實上,三維電極作為微電極,可在土壤中產(chǎn)生額外的H+和OH-,在第三極顆粒周圍形成小的酸性/堿性區(qū)域,能夠中和從主電極遷移的H+/OH-[23],從而能夠減緩?fù)寥浪峄内厔?,避免pH急劇變化。
2.3"三維電場對博落回鈾富集性能的影響
不同處理組博落回鈾富集性能和干生物量見圖3。從圖3-a可以看出:與U+P+AC組相比,U+P+AC+C組中博落回地上部分和地下部分的U質(zhì)量分?jǐn)?shù)分別增加了17.4 %和43.3 %,富集系數(shù)提高了43.6 %。這表明三維電場對博落回鈾富集性能的提升效果較為顯著。此外,U+P+AC+C組地上、地下部分干生物量比U+P+AC組分別提高了40.4 %和37.6 %(見圖3-b)。三維電場中的導(dǎo)電炭氣凝膠電極作為微電極,不僅可以加速土壤顆粒上UO2(OH)2的解吸,提高植物根際土壤中有效態(tài)鈾的含量,從而增加植物根部對鈾的吸收[24],而且還能中和從主電極遷移的H+/OH-[25],使根際土壤的pH處于一個合適的值,更利于植物生長。
2.4"三維電場對博落回體內(nèi)抗氧化酶活性的影響
植物在受到重金屬脅迫時,體內(nèi)會產(chǎn)生大量活性自由基,部分自由基有信號傳遞的作用[26],但過多自由基堆積會對正常植物組織造成過氧化脅迫,進(jìn)而影響植物的新陳代謝[27]。不同處理組博落回的生理活性指標(biāo)見圖4。從圖4可以看出:與U+P+AC組相比,U+P+AC+C組具有較低的SOD活性與MDA活性和較高的CAT活性與POD活性,表明三維電場與博落回耦合在減輕鈾脅迫對博落回的傷害方面比二維電場更具優(yōu)勢。導(dǎo)電炭氣凝膠的缺陷位點和官能團(tuán)使其可以加速自由基氧化,為植物清除活性氧[28]。同時,電場可引起細(xì)胞內(nèi)蛋白質(zhì)、糖、脂質(zhì)等分子的定向排序,含金屬的酶形成一定的構(gòu)象,活性部位形成一個活性中心,對酶有提前激活作用,從而提高植物抗氧化性能[29-30]。因此,電場與導(dǎo)電炭氣凝膠耦合形成的三維電場能夠有效緩解鈾對博落回的過氧化脅迫。
2.5"三維電場對博落回體內(nèi)鈾及亞細(xì)胞分布的影響
不同處理組博落回根、莖、葉的細(xì)胞器中鈾質(zhì)量分?jǐn)?shù)及亞細(xì)胞分布見圖5。從圖5-a)可以看出:U+P+AC+C組博落回的根、莖、葉中鈾質(zhì)量分?jǐn)?shù)均高于U+P+AC組,說明三維電場可提高博落回對鈾的去除效果。從圖5-b)可以看出:與二維電場相比,三維電場可影響鈾在博落回細(xì)胞中的亞細(xì)胞分布,促進(jìn)鈾向博落回細(xì)胞器內(nèi)轉(zhuǎn)移,尤其根部鈾的轉(zhuǎn)移更為明顯。鈾不是博落回生長的必需元素,且植物中沒有轉(zhuǎn)運鈾的通道和轉(zhuǎn)運蛋白,但鈾可以經(jīng)由運輸必需元素的渠道進(jìn)入植物,從而被植物吸收。生物炭中存在鈣(Ca)、鉀(K)、鎂(Mg)和磷(P)等營養(yǎng)物質(zhì),可以向土壤釋放養(yǎng)分,促進(jìn)植物生長[31]。因此,導(dǎo)電炭氣凝膠材料的引入可能會刺激轉(zhuǎn)運體吸收必需元素,進(jìn)而促進(jìn)植物對鈾的吸收和轉(zhuǎn)運,使鈾轉(zhuǎn)移至博落回細(xì)胞器中。
2.6"三維電場對根際土壤中鈾形態(tài)分布的影響
土壤中鈾的化學(xué)行為和生物可利用性受鈾的化學(xué)形態(tài)影響。根據(jù)MAENPAA等[32]的研究結(jié)果,植物富集鈾的主要形態(tài)是可交換態(tài)鈾和碳酸鹽結(jié)合態(tài)鈾。不同處理組根際土壤中鈾形態(tài)分布見圖6。從圖6可以看出:與U+P+AC組相比,U+P+AC+C組的可交換態(tài)占比提高了10百分點,碳酸鹽結(jié)合態(tài)鈾占比降低了11百分點。導(dǎo)電炭氣凝膠材料可以刺激植物分泌大量的有機(jī)酸[33],從而分解土壤中部分碳酸鹽結(jié)合態(tài)鈾和鐵錳氧化物結(jié)合態(tài)鈾,使可交換態(tài)鈾的比例增加,進(jìn)而被植物吸收[34]。因此,三維電場和博落回的耦合可增強(qiáng)鈾酰離子在土壤中的流動性,提高土壤中可利用態(tài)鈾的含量,促進(jìn)博落回對鈾的去除。
3"結(jié)"論
1)三維電場耦合博落回可使博落回地上和地下部分鈾質(zhì)量分?jǐn)?shù)在U+P+AC組的基礎(chǔ)上分別提高17.4 %和43.3 %。
2)三維電場耦合博落回可使博落回體內(nèi)CAT活性、POD活性增強(qiáng),緩解鈾對植物的氧化脅迫,增強(qiáng)博落回對鈾的耐受性。
3)三維電場耦合博落回可使根際土壤中可交換態(tài)鈾提高,促進(jìn)了土壤中鈾從其他形態(tài)向生物可利用態(tài)轉(zhuǎn)變,增強(qiáng)鈾從細(xì)胞壁和可溶性部分進(jìn)入細(xì)胞器的能力。
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Experimental study "of 3D electric field enhanced
Macleaya cordata phytoremediation of uranium-contaminated soil
Liu Qian1,2,Zeng Xiangyu1,2,Ding Dexin1,2,Ma Jianhong1,2
(1.School of Resources Environment and Safety Engineering,University of South China;
2.Key Discipline Laboratory for National Defense for Biotechnology in Uranium Mining and Hydrometallurgy,
University of South China)
Abstract:In this study,pot experiments were utilized to investigate the impact of 3D electric fields on the efficacy of Macleaya cordata in remediating uranium-contaminated soil.The results indicated that compared with the 2D electric field,the coupling between the 3D electric field and Macleaya cordata could lead to an increase in uranium mass fraction in both the above-ground and underground parts of Macleaya cordata by 17.14 % and 43.3 %,and an increase in dry biomass by 40.4 % and 37.6 %,respectively.Additionally,the proportion of exchangeable uranium in the soil showed an increase of 10 percentage points.Meanwhile,the subcellular distribution of uranium within Macleaya cordata was altered,leading to increased uranium accumulation and transfer to organelles,particularly in the stems.These findings indicate that the 3D electric field can further improve the remediation performance of Macleaya cordata on uranium-contaminated soil,offering a promising approach for enhancing phytoremediation.
Keywords:3D electric field;phytoremediation;Macleaya cordata;uranium contamination;soil
;bioremediation