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淹水稻田中土壤性質(zhì)的變化及其對(duì)土壤鎘活性影響的研究進(jìn)展

2016-12-28 10:11賀前鋒桂娟劉代歡李學(xué)釗李鵬祥權(quán)勝祥
關(guān)鍵詞:氧化物稻田變化

賀前鋒,桂娟,劉代歡,李學(xué)釗,李鵬祥,權(quán)勝祥

(湖南永清環(huán)保研究院有限責(zé)任公司,長(zhǎng)沙 410330)

淹水稻田中土壤性質(zhì)的變化及其對(duì)土壤鎘活性影響的研究進(jìn)展

賀前鋒,桂娟,劉代歡*,李學(xué)釗,李鵬祥,權(quán)勝祥

(湖南永清環(huán)保研究院有限責(zé)任公司,長(zhǎng)沙 410330)

近年來,面對(duì)稻田土壤鎘(Cd)污染日益嚴(yán)重和“鎘米”事件頻發(fā)的現(xiàn)狀,許多專家對(duì)稻田土壤鎘的活性變化及其污染治理進(jìn)行了大量研究,大多數(shù)研究表明淹水能降低稻田土壤Cd的活性和稻米Cd的含量。但是,由于稻田土壤自身的復(fù)雜性以及影響因素的多樣性、綜合性和不確定性,尤其是在淹水條件下,稻田土壤性質(zhì)[土壤膠體和團(tuán)聚體、pH和Eh(pe+pH)、陰離子和陽(yáng)離子、鐵錳氧化物和含硫化合物、有機(jī)質(zhì)和可溶性有機(jī)物、碳酸鹽和磷酸鹽、根系分泌物和微生物等]發(fā)生了復(fù)雜變化,使得Cd活性變化更加復(fù)雜,Cd污染的防控和修復(fù)更加困難。通過綜述淹水條件下稻田土壤性質(zhì)的變化,闡述了這些變化對(duì)土壤中Cd活性的影響,同時(shí)對(duì)該領(lǐng)域的研究方向進(jìn)行了展望,旨在為實(shí)現(xiàn)Cd污染稻田的農(nóng)業(yè)安全生產(chǎn)提供理論依據(jù),并為Cd污染土壤的修復(fù)治理提供參考。

淹水;稻田;土壤性質(zhì);鎘活性;鎘污染

近年來,由于污水灌溉、農(nóng)藥化肥施用、礦山開采和汽車尾氣排放等,我國(guó)耕地土壤重金屬污染形勢(shì)日趨嚴(yán)峻[1]。2014年,全國(guó)土壤污染公報(bào)顯示,全國(guó)中重度污染耕地約333萬hm2,耕地土壤點(diǎn)位超標(biāo)率高達(dá)19.4%,其中以鎘(Cd)污染最為突出,樣點(diǎn)超標(biāo)率達(dá)7.0%,每年生產(chǎn)的農(nóng)產(chǎn)品中Cd含量超標(biāo)的已超過14.6×108kg[2],因Cd污染引起的糧食安全問題屢見不鮮[3]。水稻是我國(guó)第一大糧食作物,約有60%以上的人口以稻米為主食[4-5]。稻米質(zhì)量安全關(guān)系到國(guó)計(jì)民生,加快Cd污染稻田修復(fù)、保障糧食安全已迫在眉睫。

Cd主要通過土壤-作物系統(tǒng)進(jìn)入人體,而稻田土壤Cd的生物有效性即活性是影響重金屬Cd進(jìn)入人體的主要因素[6]。大量研究表明,稻米Cd含量與土壤中有效態(tài)Cd含量密切相關(guān)[1,7]。土壤有效態(tài)Cd是作物吸收的主要形式,主要包括水溶性Cd和交換態(tài)Cd。因此,降低土壤Cd活性是避免Cd通過食物鏈進(jìn)入人體,進(jìn)而危害人類健康的關(guān)鍵。

水分管理為Cd污染控制的主要農(nóng)藝調(diào)控措施之一。有研究表明,在Cd污染的稻田采用傳統(tǒng)的全生育期深水淹灌比濕潤(rùn)灌溉或間歇灌溉等節(jié)水措施更有利于降低土壤Cd生物有效性和稻米Cd含量[8-9]。土壤膠體和團(tuán)聚體、土壤pH和Eh、陰陽(yáng)離子、鐵錳氧化物和硫化合物、有機(jī)質(zhì)和可溶性有機(jī)物、碳酸鹽和磷酸鹽、根系分泌物和微生物等性質(zhì)是影響Cd生物有效性的重要因素[1,10]。在淹水條件下,這些因素會(huì)發(fā)生復(fù)雜的化學(xué)變化,進(jìn)而影響土壤Cd的形態(tài)分配[11]。目前,很多學(xué)者對(duì)淹水還原條件下土壤Cd生物有效性及其制約機(jī)理進(jìn)行了研究[11-12]。大量研究表明,隨土壤還原作用的增強(qiáng),土壤Cd活性形態(tài)的含量降低[13-14]。但是,葛瀅等[15]采用黃棕壤進(jìn)行淹水培養(yǎng)實(shí)驗(yàn),結(jié)果表明還原作用越強(qiáng),土壤有效Cd含量越高??梢姡捎诘咎锿寥佬再|(zhì)的不同以及各因素的多樣性和復(fù)雜性,淹水對(duì)土壤Cd活性轉(zhuǎn)化具有上升和下降的雙向影響。因此,探明淹水條件土壤Cd活性變化需要綜合考慮以上各因素的影響。

本文綜述了淹水條件下稻田土壤性質(zhì)[土壤團(tuán)聚體和膠體、pH和Eh(pe+pH)、陰離子和陽(yáng)離子、鐵錳氧化物和含硫化合物、有機(jī)質(zhì)和可溶性有機(jī)物、碳酸鹽和磷酸鹽、根系分泌物和微生物等]的變化,并闡述了土壤性質(zhì)的變化對(duì)土壤中Cd活性的影響,旨在為淹水稻田土壤中Cd活性的變化規(guī)律及其制約機(jī)理的研究和Cd污染稻田的治理與糧食的安全生產(chǎn)提供理論依據(jù)和技術(shù)支撐。

1 土壤性質(zhì)的變化及其對(duì)Cd活性的影響

1.1 膠體和團(tuán)聚體的變化及其對(duì)鎘活性的影響

1.1.1 膠體變化及其對(duì)Cd活性的影響

土壤膠體是指粒徑范圍在1 nm~1 μm之間的一類細(xì)微粒物質(zhì),可分為無機(jī)膠體、有機(jī)膠體和無機(jī)-有機(jī)復(fù)合膠體。膠體具有大量的比表面積和豐富的表面電荷,對(duì)Cd有強(qiáng)的吸附能力,對(duì)Cd的生物有效性有重要影響[16]。當(dāng)土壤淹水后,土壤膠體會(huì)從土壤基質(zhì)釋放到土壤溶液中或溶液中的土壤膠體沉積到土壤基質(zhì)上。有研究表明,土壤淹水后,土壤陽(yáng)離子濃度降低,與Cd對(duì)膠體吸附的競(jìng)爭(zhēng)減小,促進(jìn)土壤膠體對(duì)Cd的吸附[11,17]。

1.1.2 團(tuán)聚體變化及其對(duì)Cd活性的影響

土壤團(tuán)聚體是土壤結(jié)構(gòu)最基本的物質(zhì)和功能單元。不同粒徑的團(tuán)聚體顆粒組成、有機(jī)質(zhì)、氧化鐵及礦物質(zhì)結(jié)合方式各異,對(duì)重金屬的束縛能力及生物有效性不同[18]。龔倉(cāng)等[19]研究表明,隨團(tuán)聚體粒徑的增加Cd在團(tuán)聚體中的富集呈減弱的趨勢(shì),且主要分布在粉-黏團(tuán)聚體。郁紅艷等[20]研究了農(nóng)田土壤水穩(wěn)定性團(tuán)聚體中Cd的分布規(guī)律,表明總Cd和各化學(xué)形態(tài)Cd主要存在庫(kù)是大團(tuán)聚體和微小團(tuán)聚體。

有機(jī)質(zhì)是土壤團(tuán)聚體的膠結(jié)物質(zhì),與團(tuán)聚體的形成和功能緊密相關(guān)[21]。有研究表明,土壤中的有機(jī)碳含量隨團(tuán)聚體粒徑減小而升高,Cd分布與顆粒有機(jī)碳含量正相關(guān)[22]。淹水后,土壤有機(jī)質(zhì)累積,水穩(wěn)定性團(tuán)聚體更加穩(wěn)定,對(duì)Cd的吸附增強(qiáng)[23]。

1.2 pH、Eh和pe+pH的變化及其對(duì)Cd活性的影響

1.2.1 pH和Eh變化及其對(duì)Cd活性的影響

淹水使稻田土壤與空氣隔絕,隨土壤中微生物的代謝,土壤中氧氣迅速減少;微生物分解土壤有機(jī)質(zhì)釋放大量的電子和質(zhì)子,使硝態(tài)氮、鐵錳氧化物等氧化性物質(zhì)接受電子發(fā)生還原,同時(shí)也消耗大量的質(zhì)子,導(dǎo)致pH值向中性靠攏,即酸性土壤pH值升高及堿性土壤pH值降低,而氧化還原電位(Eh)在兩種土壤中均下降,尤其在淹水初期,變化顯著[24-25]。根據(jù)黃丹丹等[26]研究結(jié)果作出淹水過程中酸性紅壤土和堿性潮黃土pH和Eh的變化圖形,如圖1所示。

pH變化跟土壤本底性質(zhì)相關(guān)。淹水條件下,酸性土壤pH之所以升高,主要是因?yàn)橥寥黎F氧化物的還原溶解作用,而堿性土壤pH降低則主要由土壤中大量碳酸鹽溶解作用以及土壤中CO2的累積所導(dǎo)致[27]。土壤pH值能夠影響土壤對(duì)Cd的吸附,吸附曲線可分為3個(gè)區(qū)間:低pH值低吸附區(qū),中pH值穩(wěn)定增長(zhǎng)區(qū)及高pH值強(qiáng)吸附區(qū)[28]。pH值小于3.2時(shí),Cd的吸附率很低;pH在4.5~7.2時(shí),Cd的吸附率與pH呈顯著正相關(guān);pH大于7.5時(shí),Cd的吸附率接近100%,主要以氧化物結(jié)合態(tài)及殘?jiān)鼞B(tài)形式存在[28]。大量研究也表明,土壤pH與稻谷Cd含量成反比[26,29]。

Eh值反映土壤氧化還原程度。一般認(rèn)為在pH為7的土壤中,Eh值高于125 mV時(shí),土壤以氧化狀態(tài)為主;Eh值低于125 mV時(shí),土壤以還原狀態(tài)為主[30]。稻田淹水時(shí),土壤耕作層水分飽和,土壤處于還原狀態(tài)。在低Eh值下,土壤Cd更易于由有效態(tài)轉(zhuǎn)化為穩(wěn)定態(tài),從而降低Cd的活性[31]。

圖1 土壤淹水后pH和Eh變化Figure 1 The change of pH and Eh of the soil after flooding

1.2.2 pe+pH的變化及其對(duì)鎘活性的影響

pe表示參加反應(yīng)的電子活度的負(fù)對(duì)數(shù),pH表示參加反應(yīng)的質(zhì)子活度的負(fù)對(duì)數(shù)。氧化還原反應(yīng)有電子的轉(zhuǎn)移和質(zhì)子的參與,因而pe+pH能更好地表示參加化學(xué)和電化學(xué)反應(yīng)的反應(yīng)物與生成物的濃度變化[26]。pe+pH值越小,表示還原勢(shì)越強(qiáng),pe+pH值越大則氧化勢(shì)越強(qiáng)。土壤淹水后,土壤還原程度加強(qiáng),pe+ pH值下降,且土壤類型不同,下降的程度也不同[32]。李義純等[32]研究表明(圖2),在淹水過程中黃潮土比紅壤土pe+pH下降程度更大。

pe+pH值可用來表征土壤鐵礦物的形態(tài)轉(zhuǎn)化,其變化影響土壤Cd的形態(tài)[33]。淹水使酸性土壤pe+pH下降,Cd活性降低,主要受土壤鐵氧化物控制;淹水使堿性土壤pe+pH下降,Cd活性降低,主要受土壤碳酸鐵控制[33]。隨著pe+pH下降,土壤Cd由可交換態(tài)轉(zhuǎn)化成其他形態(tài),且Cd固相組分逐級(jí)發(fā)生變化[33]。在pe+pH為14.16~11.34、pH<5.0時(shí),土壤Cd組分以可交換態(tài)Cd為主;在pe+pH為14.16~6.04、pH>5.0時(shí),土壤Cd組分以碳酸鹽態(tài)和氧化物結(jié)合態(tài)為主;在pe+pH為6.48~5.38、pH>5.78時(shí),土壤Cd組分以有機(jī)結(jié)合態(tài)為主;pe+pH<5時(shí),土壤Cd組分以硫化物為主[34]。

圖2 土壤淹水后pe+pH變化Figure 2 The change of pe+pH of the soil after flooding

1.3 陰離子和陽(yáng)離子的變化及其對(duì)Cd活性的影響

1.3.1 陰離子的變化及其對(duì)Cd活性的影響

1.3.2 陽(yáng)離子的變化及其對(duì)Cd活性的影響

土壤陽(yáng)離子主要有K+、Al3+、Ca2+、Mg2+和Fe2+[10]。土壤陽(yáng)離子與Cd2+之間存在土壤表面吸附點(diǎn)位的競(jìng)爭(zhēng)。在淹水條件下,非變價(jià)元素Al3+、Ca2+、Mg2+和K+含量基本不變但飽和度降低,因此與Cd2+對(duì)土壤表面吸附點(diǎn)的競(jìng)爭(zhēng)減少,Cd活性降低。變價(jià)元素Fe由于氧化鐵(Ⅲ)的還原溶解造成Fe(Ⅱ)濃度的增加,而土壤鐵形態(tài)的變化影響Cd的鐵錳結(jié)合態(tài)的變化,從而控制Cd活性的變化。陳莉娜等[41]研究淹水還原作用對(duì)紅壤Cd生物有效性的影響,水溶性Fe(Ⅱ)濃度在淹水前期增大而后期降低,Cd的生物有效性在淹水初期高于后期。

1.4 鐵錳氧化物和含硫化合物的變化及其對(duì)Cd活性的影響

1.4.1 鐵錳氧化物的變化及其對(duì)Cd活性的影響

水稻土壤中最為豐富的金屬氧化物是鐵氧化物,包括晶型的赤鐵礦、磁鐵礦、針鐵礦、纖鐵礦和無定形的水鐵礦,且還原溶解作用依次降低。土壤淹水后,鐵氧化物發(fā)生還原溶解,水溶性Fe2+濃度增加,同時(shí),F(xiàn)e2+形成FeCO3、Fe(OH)2、Fe3(OH)8等沉淀[42]。尤其在有機(jī)質(zhì)和豐富的土壤,F(xiàn)e2+與S2-反應(yīng)形成黑色FeS[43]。這些沉淀又被氧化為溶解度較低的無定形氧化鐵,導(dǎo)致無定形氧化鐵濃度增加[42]。

土壤鐵氧化物的變化是影響Cd活性的重要因素。一方面,鐵氧化物具有較大的比表面積和可變表面電荷,對(duì)土壤中的Cd有很大的吸附容量[44],因此在淹水條件下,鐵氧化物還原溶解也是其自身對(duì)Cd的釋放;另一方面,不同的鐵氧化物具有不同的表面活性吸附點(diǎn)位,對(duì)Cd的吸附也不同[45],因此Fe形態(tài)的再分配決定了Cd形態(tài)的再分配。有研究表明,土壤淹水后可交換態(tài)Cd占總Cd的比例明顯下降,且下降的部分向活性較低的晶形鐵氧化物結(jié)合態(tài)轉(zhuǎn)化[46]。

錳的各種氧化態(tài)隨化學(xué)價(jià)的升高,堿性減弱而酸性增強(qiáng)。低價(jià)的MnO、Mn2O3屬堿性,4價(jià)的MnO2屬中性,高價(jià)的MnO3、Mn2O7為酸性。在酸性土壤中,因?yàn)檠退鹑毖踉斐裳趸€原點(diǎn)位較低時(shí),氧化錳氧化成易溶于水的Mn(Ⅱ)。Fulda等[47]研究認(rèn)為,在淹水還原環(huán)境,溶解還原的Mn2+阻止水稻對(duì)Cd的吸收。Kashem等[48]研究發(fā)現(xiàn),淹水后交換態(tài)Cd的含量明顯下降而鐵錳氧化物結(jié)合態(tài)Cd的含量顯著增加,推測(cè)其主要原因是新形成的鐵錳礦物對(duì)Cd的吸附,導(dǎo)致Cd由交換態(tài)向鐵錳氧化物結(jié)合態(tài)轉(zhuǎn)化。

另外,值得強(qiáng)調(diào)的是,在淹水厭氧環(huán)境下,鐵錳氧化物在水稻根表形成一種紅色或紅棕色氧化物膠膜[49]。此膠膜對(duì)土壤Cd具有吸附和吸收作用,從而促進(jìn)[50]、阻止[51]或者不影響[52]水稻對(duì)土壤Cd的吸收,其作用方向和程度主要取決于膜的形成量、老化程度以及水稻品種對(duì)Cd的富集和轉(zhuǎn)運(yùn)能力[53]??梢姡退畢捬醐h(huán)境可促進(jìn)根系鐵錳氧化物的形成,而此膜對(duì)土壤Cd活性的影響受多個(gè)因素的限制。

1.4.2 含硫化合物的變化及其對(duì)鎘活性的影響

稻田淹水條件下,土壤形成還原環(huán)境促進(jìn)土壤中揮發(fā)性硫化物(AVS,如H2S)或者硫酸鹽(SO2-4)還原,生成的S2-或-HS與土壤中Cd形成穩(wěn)定、難溶的CdS沉淀。因此,CdS的生成可顯著降低土壤中Cd的活性[8,54]。有研究表明,當(dāng)水稻土壤淹水5周時(shí),S2-和Cd2+的離子活度積接近CdS的溶度積,表明淹水土壤中有CdS沉淀生成[55]。劉邵兵等[8]研究表明,Cd污染稻田土壤中有效硫及其還原性S2-的形成是顯著影響水稻吸收累積Cd的一個(gè)間接因子。也有研究表明,在還原性強(qiáng)的土壤中,當(dāng)pe+pH小于5時(shí),才有可能生成CdS[26]。但目前關(guān)于Cd與硫化物之間的作用機(jī)制并不清楚。一方面,硫化合物提供的S2-與Cd2+結(jié)合生成CdS,從而降低土壤Cd的活性;另一方面,S2-與土壤鐵形成鐵的硫化物,Cd2+再與鐵的硫化物發(fā)生共沉淀從而導(dǎo)致Cd活性的降低[56-57]。

1.5 有機(jī)質(zhì)和可溶性有機(jī)物的變化及其對(duì)Cd活性的影響

1.5.1 有機(jī)質(zhì)的變化及其對(duì)Cd活性的影響

與通氣良好的土壤相比,淹水土壤中O2的減少,可降低有機(jī)質(zhì)的分解速率,從而導(dǎo)致有機(jī)質(zhì)的累積[58]。一方面,有機(jī)質(zhì)通過改變土壤負(fù)電荷量、pH等理化性質(zhì)以提高土壤對(duì)Cd的吸附;另一方面,有機(jī)質(zhì)具有大量的功能團(tuán),對(duì)Cd2+具有螯合作用,可導(dǎo)致Cd活性降低[59]。但有機(jī)質(zhì)對(duì)土壤Cd的影響不穩(wěn)定,隨著有機(jī)質(zhì)的分解,吸附的Cd會(huì)釋放出來,并向交換態(tài)Cd轉(zhuǎn)化,提高Cd的活性[60]。

1.5.2 可溶性有機(jī)物的變化及其對(duì)Cd活性的影響

對(duì)于稻田生態(tài)系統(tǒng),淹水后土壤有機(jī)質(zhì)的分解使可溶性有機(jī)物(DOM)大量溶出[61]。DOM具有比土壤更多的吸附點(diǎn)位,可以作為土壤重金屬的“配位體”和“遷移載體”[62]。它可以提供一系列螯合能力不同的結(jié)合點(diǎn)位與Cd螯合,形成有機(jī)-重金屬離子配合物,從而提高土壤中Cd的溶解性[63]。有研究發(fā)現(xiàn),DOM與Cd2+螯合形成的水溶性絡(luò)合物,可提高Cd的活性和遷移能力,降低土壤對(duì)Cd的吸附[64]。也有報(bào)道認(rèn)為,Cd溶解度增大的原因在于DOM通過與Cd2+競(jìng)爭(zhēng)土壤表面的吸附點(diǎn)位,從而減少土壤對(duì)Cd2+的吸附[65]。但也有相反的研究發(fā)現(xiàn),在較強(qiáng)酸性土壤中,土壤帶有很強(qiáng)正電荷,土壤對(duì)DOM的吸附致使自身的負(fù)電荷增加,進(jìn)而促進(jìn)土壤對(duì)Cd2+的吸附。同時(shí),DOM在Cd2+與土壤之間的螯合橋梁作用也會(huì)增大Cd2+在土壤表面的吸附量[66],導(dǎo)致Cd的溶解度減小。DOM對(duì)土壤Cd的活性有增大和減小的雙重影響,可能與土壤類型和DOM種類等有關(guān)。

1.6 碳酸鹽和磷酸鹽的變化及其對(duì)Cd活性的影響

1.6.1 碳酸鹽的變化及其對(duì)Cd活性的影響

在稻田土壤中,主要的碳酸鹽有Na2CO3、CaCO3、MnCO3和FeCO3,且一般存在于中性或堿性土壤中。許多研究表明,碳酸鹽對(duì)Cd有較強(qiáng)的吸附能力,且CdCO3的形成本身就能降低土壤中Cd的溶解度[10,67]。

當(dāng)?shù)咎镅退畷r(shí),碳酸鹽溶解可導(dǎo)致水體pH下降和大量鹽基離子溶出[68]。由于此過程相對(duì)緩慢,碳酸鹽一直被視為淹水土壤的“定時(shí)炸彈”。水體pH下降使土壤表面負(fù)電荷數(shù)減少,進(jìn)而導(dǎo)致土壤對(duì)Cd2+的吸附量減少;同時(shí),溶出的大量鹽基離子與Cd2+競(jìng)爭(zhēng)土壤表面吸附點(diǎn)位,也導(dǎo)致土壤對(duì)Cd2+的吸附量減少,Cd活性提高[10]。因此,在堿性或中性稻田土壤中,碳酸鹽通過影響土-水體系的pH和溶液中鹽基離子的含量,間接影響土壤中Cd的活性。

1.6.2 磷酸鹽的變化及其對(duì)鎘活性的影響

土壤中的磷酸鹽可分為與Fe、Al、Ca等結(jié)合的化合態(tài)磷酸鹽和吸附在有機(jī)物或黏土礦物表面的吸附態(tài)磷酸鹽。磷酸鹽穩(wěn)定Cd的作用機(jī)理主要是表面直接吸附、誘導(dǎo)吸附或者與Cd生成沉淀或礦物等復(fù)雜反應(yīng)[69]。

土壤淹水后化合態(tài)磷酸鹽溶解。由于相比其他磷酸鹽,磷酸鎘鹽的溶解度較低,在不同的pH條件下,磷酸鹽與Cd2+結(jié)合可生成Cd(H2PO4)2、CdHPO4或Cd3(PO4)2更穩(wěn)定的化合物,土壤Cd活性降低[70]。此外,有研究表明,磷酸鹽被新形成的具有巨大表面積和更多吸附位點(diǎn)的無定形鐵氧化物所吸附,從而增加土壤磷酸鹽的吸附量,引起土壤表面負(fù)電荷增加,誘導(dǎo)Cd的吸附增加[71]。但有研究表明淹水影響水稻土對(duì)磷酸鹽的吸附不是連續(xù)的,淹水后期在一個(gè)特定的吸附磷酸鹽水平,還原狀態(tài)土壤溶液中磷酸鹽溶解大于吸附,導(dǎo)致Cd的溶解增加[72]。

1.7 根系化合物和微生物的變化及其對(duì)Cd活性的影響

1.7.1 根系化合物的變化及其對(duì)Cd活性的影響

根系分泌物包括低分子量化合物(氨基酸、有機(jī)酸等)和高分子量化合物(類金屬蛋白、粘膠等)。這些化合物可通過酸化、螯合、絡(luò)合以及活化等過程改變土壤Cd的形態(tài),從而影響Cd的活性[73]。

淹水土壤通透性、pH等性質(zhì)的變化都會(huì)影響根系分泌物活化Cd。在淹水條件下,根系分泌物可以通過分泌質(zhì)子或還原性有機(jī)酸,使根際pH降低,酸化土壤中不溶態(tài)Cd[74]。水稻根系的分泌物也能溶解鐵錳氧化物膜,從而影響水稻對(duì)Cd的吸收[75]。此外,根系分泌物中某些金屬結(jié)合蛋白和某些特殊的有機(jī)酸(如蘋果酸、檸檬酸)也能螯合Cd,形成穩(wěn)定的螯合物。例如根分泌的粘膠物質(zhì)與根際的Cd2+結(jié)合,形成穩(wěn)定的螯合體,將污染物Cd固定在土壤中[76]。

1.7.2 微生物的變化及其對(duì)Cd活性的影響

微生物對(duì)Cd的修復(fù)機(jī)理主要是生物吸附和生物轉(zhuǎn)化[77]。此外,微生物還可通過分泌質(zhì)子、有機(jī)酸、鐵載體等物質(zhì)或者將大分子分泌物轉(zhuǎn)化成小分子化合物,活化土壤Cd[78]。

土壤淹水后,微生物群落結(jié)構(gòu)發(fā)生變化[61]。淹水還原條件有利于厭氧型微生物的生長(zhǎng),如硫酸鹽還原菌和異化鐵還原菌等。硫酸鹽還原菌可將土壤中的還原成S2-,S2-與Cd2+結(jié)合生成CdS沉淀,使土壤Cd活性降低[79]。異化鐵還原菌在厭氧生長(zhǎng)環(huán)境下能結(jié)合并氧化有機(jī)物以其作為電子供體,同時(shí)將Fe(Ⅲ)還原成Fe(Ⅱ)。黃森等[80]研究了淹水時(shí)間對(duì)水稻土中4種異化鐵還原功能菌豐度的影響,結(jié)果表明Fe(Ⅱ)濃度在整個(gè)淹水培養(yǎng)期增加。在淹水前期,同屬發(fā)酵型的梭菌和芽孢桿菌豐度上升,對(duì)鐵還原的貢獻(xiàn)較大;在培養(yǎng)后期,地桿菌和厭氧粘粉菌成為Fe(Ⅱ)濃度持續(xù)增長(zhǎng)的重要因素。因此,異化鐵還原菌通過影響Fe的還原而影響對(duì)Cd的吸附。

2 總結(jié)與展望

綜上可知,由于淹水稻田土壤自身的復(fù)雜性、影響因素的多樣性、不確定性以及各因素之間的綜合性,有關(guān)淹水稻田土壤性質(zhì)的變化及其對(duì)土壤Cd活性影響的研究常出現(xiàn)不同的研究結(jié)果。一方面,淹水條件下,土壤膠體、團(tuán)聚體、鐵錳礦物、固相有機(jī)質(zhì)、磷酸鹽對(duì)Cd的吸附、酸性土壤pH的升高和氧化還原電位(Eh)的降低、根際鐵錳氧化膜的阻礙、硫化物與Cd2+的共沉淀、還原菌的還原作用以及根系分泌物的螯合作用都可能導(dǎo)致Cd活性降低;另一方面,陰離子(如Cl-和)與Cd2+之間的配位、鐵錳礦物和碳酸鹽的溶解、根際氧化膜的吸附、DOM與Cd2+的螯合以及根系分泌物的活化作用都可能導(dǎo)致Cd活性升高。以上制約因素對(duì)土壤Cd活性變化影響的不同可能跟稻田生態(tài)系統(tǒng)的復(fù)雜環(huán)境有關(guān),也給土壤Cd污染治理的研究帶來困難。

目前,大量的研究集中在淹水對(duì)土壤理化性質(zhì)的影響方面,缺乏結(jié)合生物指標(biāo)以及不同生長(zhǎng)期Cd在土壤-作物系統(tǒng)中遷移轉(zhuǎn)化的系統(tǒng)性研究。為進(jìn)一步探索淹水稻田土壤中Cd活性變化的機(jī)理,為稻田Cd污染控制和治理提供科學(xué)依據(jù),今后的研究可從以下三個(gè)方面來開展:首先,結(jié)合作物生長(zhǎng)季節(jié)對(duì)土壤多種指標(biāo),尤其是生物指標(biāo)(如藻類等小型微生物)進(jìn)行監(jiān)測(cè),研究不同水稻生長(zhǎng)期淹水稻田土壤性質(zhì)的變化及其對(duì)Cd活性的影響,揭示影響稻田土壤Cd形態(tài)和活性變化的主導(dǎo)因素和內(nèi)在調(diào)控機(jī)制。其次,研究淹水條件下Cd在稻田土壤-作物中的遷移,揭示污染稻田土壤-作物系統(tǒng)Cd的遷移轉(zhuǎn)化機(jī)理。第三,將國(guó)內(nèi)外先進(jìn)儀器和分析手段(原子力顯微技術(shù)、X射線熒光光譜原位監(jiān)測(cè)技術(shù)、污染源解析技術(shù)等)應(yīng)用于研究,在不破壞土壤結(jié)構(gòu)的前提下對(duì)土壤重金屬污染進(jìn)行快速、精準(zhǔn)檢測(cè),這對(duì)加快農(nóng)田生態(tài)系統(tǒng)Cd污染的防控與修復(fù)具有重要意義。

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Research progress of soil property′s changes and its impacts on soil cadmium activity in flooded paddy field

HE Qian-feng,GUI Juan,LIU Dai-huan*,LI Xue-zhao,LI Peng-xiang,QUAN Sheng-xiang
(Hunan Yonker Environmental Protection Research Institute Co.,Ltd.,Changsha 410330,China)

Soil is the first line of defense to protect the crop safety,and the material basis for the human food quality and ecological environmental security.Since soil cadmium(Cd)pollution in paddy field and“Cd-polluted rice”issue become more severe in recent years,more and more researches focus on the changes of soil Cd activity and its pollution restoration.Previous results showed that submerged condition could help decrease soil Cd activity in soil and also lower the Cd content in rice.However,due to the complexity of the soil,and the diversity,comprehensiveness and uncertainty of external factors,especially under submerged condition,soil properties may have complex change. On one hand,the adsorption of soil colloid,aggregate,iron/manganese oxides,organic matters and phosphate,the rise of soil pH and reduction of Eh,the obstruction of oxide plaque on root surface,the coprecipitation of sulfide,the reduction of reducing bacteria,and the chelation of root exudates could lead to reduce Cd activity.On the other hand,the coordination of anions,the dissolution of iron/manganese oxides and carbonates,the adsorption of oxide plaque,the chelation of DOM,and activation of root exudates could increase Cd activity.These changes make the movement and transformation of Cd more complex,which may increase difficulty of Cd remediation in soil.In this paper,we summarized the changes of soil property and their effects on soil Cd activity in flooded paddy field,as well as pointed out future research directions.This paper could help provide theoretical basis for the agricultural production safety and references for Cd pollution remediation in paddy field.

flooding;paddy soil;soil property;Cd activity;Cd pollution

X53

A

1672-2043(2016)12-2260-09

10.11654/jaes.2016-0892

賀前鋒,桂娟,劉代歡,等.淹水稻田中土壤性質(zhì)的變化及其對(duì)土壤鎘活性影響的研究進(jìn)展[J].農(nóng)業(yè)環(huán)境科學(xué)學(xué)報(bào),2016,35(12):2260-2268.

HE Qian-feng,GUI Juan,LIU Dai-huan,et al.Research progress of soil property′s changes and its impacts on soil cadmium activity in flooded paddy field[J]. Journal of Agro-Environment Science,2016,35(12):2260-2268.

2016-07-06

湖南省科技計(jì)劃項(xiàng)目(2016TP2018)

賀前鋒(1979—),男,碩士,工程師,主要研究方向?yàn)榄h(huán)境污染控制。E-mail:qianfeng.he@yonker.com.cn

*通信作者:劉代歡E-mail:36882233@qq.com

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