黃巧義, 唐拴虎， 盧 瑛， 張發(fā)寶， 楊少海

(1 廣東省農(nóng)業(yè)科學(xué)院農(nóng)業(yè)資源與環(huán)境研究所，農(nóng)業(yè)部南方植物營養(yǎng)與肥料重點(diǎn)實(shí)驗(yàn)室，廣東省養(yǎng)分資源循環(huán)利用與耕地保育重點(diǎn)實(shí)驗(yàn)室，廣州 510640； 2 華南農(nóng)業(yè)大學(xué)資源環(huán)境學(xué)院，廣州 510642)

1 ASS的形成條件和過程

ASS形成過程中的鐵(Fe)、 硫(S)生物地球化學(xué)循環(huán)，在全球物質(zhì)循環(huán)過程中具有重要地位，一直是人們關(guān)注的熱點(diǎn)[17]。ASS的成土母質(zhì)為富含還原性硫化物的沉淀物，當(dāng)硫化物被氧化后形成硫酸及一系列次生鐵礦物。ASS成土過程中包含 還原性硫化物(硫化鐵為主)沉淀物成土母質(zhì)的形成，以及成土母質(zhì)的氧化兩個(gè)關(guān)鍵階段[1, 18]。發(fā)育完全的ASS土壤剖面上，常呈現(xiàn)兩種性質(zhì)截然不同的土層， 下層富含黃鐵礦的中性土壤(還原環(huán)境)，也稱潛在酸性硫酸鹽土(Potential Acid Sulfate Soils, PASS)，上層富含黃鐵礦氧化產(chǎn)物的酸性土壤(氧化環(huán)境)，也稱實(shí)際酸性硫酸鹽土(Actual Acid Sulfate Soils, AASS)[18-19]。

1.1 ASS成土母質(zhì)的形成條件與過程

Fe2++H2S→FeS+2H+

[1]

Fe2++2HS→Fe(HS)2→FeS+H2S

[2]

FeS1.1(代表亞穩(wěn)定態(tài)硫化亞鐵礦物)+H2S→FeS2+H2(完全厭氧條件)

[3]

[4]

1.2 ASS成土母質(zhì)的氧化

形成于還原條件的ASS成土母質(zhì)，因自然條件變化或者人為干擾等影響，使其環(huán)境氧化還原電位提高，ASS成土母質(zhì)被氧化而形成ASS[1, 33]。例如，北歐地區(qū)因均衡性地殼上升及農(nóng)用埋管排水的綜合作用使全新世形成的富含還原態(tài)Fe-S礦物的成土母質(zhì)被氧化形成了ASS[34]；泰國曼谷平原則因海岸線的變遷而形成帶狀A(yù)SS[6]。而干旱是導(dǎo)致塞爾維亞、 幾內(nèi)亞(比紹)等非洲國家ASS發(fā)育形成的主要因素[6]。

ASS成土母質(zhì)接觸氧氣后，還原態(tài)硫化鐵類礦物[亞穩(wěn)定態(tài)硫化亞鐵礦物(FeS1.1)和黃鐵礦(FeS2)]發(fā)生氧化反應(yīng)，其反應(yīng)式為5和6[32, 34]。FeS1.1的反應(yīng)動(dòng)力學(xué)較快，而黃鐵礦慢[34]。溶解態(tài)O2和Fe3+是該反應(yīng)主要的氧化劑，最初氧化產(chǎn)物為元素硫(S0)[32, 35-36]。FeS1.1和FeS2被氧化的過程中，形成多種形態(tài)硫、 鐵礦物，并產(chǎn)生硫酸、 H+，最終形成酸性極強(qiáng)、 生長障礙因素多及生態(tài)危害大的ASS[18, 34, 37]。

10FeS1.1(代表亞穩(wěn)定態(tài)硫化亞鐵礦物)+24O2+26H2O→10Fe(OH)3+11H2SO4

[5]

4FeS2+15O2+14H2O→4Fe(OH)3+8H2SO4

[6]

1.3 紅樹林與ASS

2 ASS中硫的演變

2.1 ASS中硫礦物的動(dòng)態(tài)變化

4FeS+3O2+6H2O→4Fe(OH)3+4S0

[7](PAS)

FeS+S0→FeS2

[8](PAS)

[9](PASTZ)

[10](ASTZ)

[11](AS)

[12](AS)

CaCO3+H2SO4+H2O→CaSO4·2H2O+CO2

[13](AS)

PASS的氧化還原電位低，只有熱力學(xué)穩(wěn)定性較差的FeS1.1能被氧化，生成氫氧化鐵和元素硫S0，尚無酸形成，土壤pH仍較高，反應(yīng)式為7[46]。在該pH條件下，元素硫S0又能與土壤中殘余的FeS1.1反應(yīng)，形成黃鐵礦(反應(yīng)式8)[29, 47]。接近PASS的TZ區(qū)域，氧化還原電位仍較低，只有少量黃鐵礦被完全氧化(反應(yīng)式9)，生成硫酸根及氫氧化鐵，但該反應(yīng)速度緩慢，不能使土體酸化[48-50]。而接近上層AASS的TZ區(qū)域，土壤pH下降到4.5以下，F(xiàn)e3+溶解度提高，成為黃鐵礦氧化反應(yīng)的主要氧化劑，進(jìn)一步加快黃鐵礦氧化(反應(yīng)式10)[32, 50]。同時(shí)，在該pH條件下，嗜酸氧化亞鐵硫桿菌催化Fe2+氧化形成Fe3+，加快催化該氧化反應(yīng)；但當(dāng)pH下降到3.5以下時(shí)，大部分釋放出的Fe3+被水結(jié)合，形成氫氧化鐵沉淀[3, 51]。AASS中黃鐵礦氧化產(chǎn)生大量硫酸，但大部分被淋溶出土體，當(dāng)土壤進(jìn)一步酸化(pH低于4.0)，硫酸根與Fe、 K、 Na等元素形成黃鉀鐵礬[KFe3(SO4)2(OH)6][52]和施氏礦物[Fe8O8(OH)6SO4][53]，尤以黃鉀鐵礬最普遍，其形成過程為反應(yīng)式11[52]。黃鉀鐵礬和施氏礦物最終被水化形成針鐵礦(FeOOH)，同時(shí)釋放出硫酸和酸(反應(yīng)式12)[53-55]。開墾耕種的ASS土壤上，常表施石灰，能中和土壤部分酸并生成石膏(反應(yīng)式13)[32]。

2.2 ASS中各種硫形態(tài)含量

3 ASS中鐵(Fe)的地球化學(xué)動(dòng)態(tài)

3.1 ASS中鐵礦物的轉(zhuǎn)化

[14]

FeS1.1(s)+H2S(aq)→FeS2(s)+H2(g)

[15]

FeS1.1(s)+Sn+1(aq)2-→FeS2(s)+Sn(aq)2-

[16]

[17]

Fe8O8(OH)6SO4+2.5H2O→8FeOOH+

[18]

[19]

圖1 黃鐵礦氧化途徑及可能產(chǎn)物Fig.1 Steps in pyrite oxidation and possible secondary Fe minerals that may form as weathering products

3.2 ASS中各種鐵礦物含量

4 ASS的酸特性

5 ASS的生態(tài)環(huán)境效應(yīng)

淹水還原環(huán)境下，由于存在硫化物、 有機(jī)物質(zhì)，有利于ASS形成金屬硫化物和金屬含量較高的有機(jī)復(fù)合物，將游離的金屬固定下來，實(shí)現(xiàn)海水凈化[86-87]。在氧化環(huán)境下，ASS嚴(yán)重酸化，Al、 Cd、 Mn、 Ni、 As等有毒金屬及類金屬大量活化[88-93]，另一方面，P、 Ca、 Mg、 Zn、 Cu、 K、 B等生物生長必需營養(yǎng)元素被固定或流失[58, 94-96]，嚴(yán)重毒害實(shí)地植物、 動(dòng)物生長。同時(shí)，酸根離子和有毒金屬及類金屬隨水經(jīng)滲漏、 側(cè)流等途徑進(jìn)入周邊水系，酸化污染周邊水體環(huán)境[15, 97-99]，及水系周邊生態(tài)系統(tǒng)[73, 100]。另外，淹水環(huán)境中因潮汐、 作物根系作用以及生物擾動(dòng)等影響，也會(huì)發(fā)生氧化反應(yīng)，使還原性硫化物發(fā)生氧化，釋放出酸根離子和金屬或類金屬，進(jìn)而污染海水環(huán)境、 危害濱海生物[101-104]。因此，ASS生態(tài)系統(tǒng)在不同環(huán)境條件扮演著環(huán)境金屬和類金屬凈化者和污染者的雙重角色，而從土壤學(xué)家的角度出發(fā)，ASS主要是環(huán)境污染源。

5.1 ASS中有毒金屬和類金屬的活性及流失風(fēng)險(xiǎn)

ASS產(chǎn)生的酸性離子以及活化的有毒金屬和類金屬隨地表徑流、 側(cè)滲、 淋溶等途徑進(jìn)入地下水、 周邊河流，污染水體質(zhì)量[11, 51, 94, 97, 100, 108-109]。ASS影響周邊水體生態(tài)，一方面因水體本身受污染，導(dǎo)致水生生物生長受害，影響水產(chǎn)養(yǎng)殖[13, 78, 97]，且以受污染水灌溉、 飲用等用途的農(nóng)戶，其身體健康也將受到威脅[6, 7, 110]；另一方面，污染水的流動(dòng)、 利用，進(jìn)一步將污染擴(kuò)大到周邊環(huán)境，加上金屬的移動(dòng)性及生物累積效應(yīng)，致使ASS的污染區(qū)域不斷擴(kuò)大。因此，ASS作為一個(gè)潛在或現(xiàn)有的環(huán)境隱患，若開發(fā)不當(dāng)將引發(fā)嚴(yán)重的生態(tài)環(huán)境問題[6]。

ASS導(dǎo)致的Fe、 Al、 Mn、 Cd等重金屬的污染已有目共睹[13, 89, 90, 111-112]，而且有些改良措施雖然中和了土壤酸性且固定Al、 Mn、 Ni和Zn等潛在的有毒金屬，但卻導(dǎo)致As和Fe的活化[13, 113]。同時(shí)，F(xiàn)e-S礦物對痕量元素的生物有效性影響顯著，已有研究表明，ASS中Fe礦物的轉(zhuǎn)化影響土壤中稀土元素的含量及分布[114]，同時(shí)，受ASS影響的江河沉淀物中，痕量元素的含量及活性明顯較高[115-116]。

5.2 ASS對實(shí)地及周邊生物的影響

ASS對植物生長的毒害不僅因低pH的直接影響，還與Al、 Fe等金屬離子活化的毒害作用有關(guān)[117]，同時(shí)，P、 Ca、 Mg、 Zn、 Cu、 K、 B等營養(yǎng)元素有效性低、 土壤結(jié)構(gòu)差等因素均限制了植物的生長[6, 118]。我國受ASS影響的水稻產(chǎn)量遠(yuǎn)低于全國平均水平，印度尼西亞、 泰國、 幾內(nèi)亞比紹、 斯里蘭卡等國家ASS稻區(qū)的產(chǎn)量也較低[6]。更有甚者，因長期酸害影響，植被無法生存，土表裸露[119]。據(jù)調(diào)查，ASS上牧草、 橡樹的Co、 Ni、 Mn含量均較常規(guī)值高[97, 120]。但F?ltmarsch等發(fā)現(xiàn)ASS中重金屬淋溶流失的比例較大，僅少量被土壤上生長的包菜吸收，因此，重金屬對實(shí)地植物的影響相對較小[121]。有研究表明，受ASS影響的奶牛的牛奶中Al含量明顯偏高，但動(dòng)物體內(nèi)金屬含量與ASS的關(guān)系尚不清晰[97]。

受ASS影響的水域中水生苔蘚體內(nèi)Al、 Cu、 Fe含量顯著高于常規(guī)值[97]。澳大利亞東部受ASS影響的流域常發(fā)生大規(guī)模魚類死亡事件，其原因主要?dú)w結(jié)于強(qiáng)酸和金屬離子含量高[122]。另一方面，魚類蛋黃、 卵子形成和產(chǎn)卵的過程受到該惡劣環(huán)境干擾而導(dǎo)致繁殖失敗，使部分魚類絕種滅亡[122]，同時(shí)，離子調(diào)節(jié)系統(tǒng)和器官呼吸作用受到破壞使魚類行為失常[97]。Faltmarsch 等[97]認(rèn)為ASS可能還影響區(qū)域的老人癡呆癥、 帕金森等神經(jīng)性疾病和心血管疾病的發(fā)生率。有學(xué)者對澳大利亞ASS土地上的房地產(chǎn)開發(fā)后的表土、 粉塵及水樣調(diào)查表明，其金屬含量及活性均在生態(tài)臨界值以內(nèi)[7]。Hinwood 等[110]調(diào)查ASS區(qū)域居民尿液、 腳趾甲及頭發(fā)中重金屬累積情況，結(jié)果表明Al、 As、 Cd、 Pb、 Cu及Zn的含量并不高。ASS對人類身體健康的影響已逐漸引起學(xué)者的關(guān)注，但目前相關(guān)證據(jù)尚不確鑿。

6 展望

1) ASS中Fe-S演變、 循環(huán)一直是人們關(guān)注的熱點(diǎn)。因沉積微環(huán)境下各種條件的不同，黃鐵礦形成途徑、 形態(tài)不一致，不同來源、 形態(tài)的黃鐵礦發(fā)育的過程也有所差異。我國前期學(xué)者對發(fā)育于紅樹林景觀的ASS研究較多，忽視了非紅樹林海濱沼澤地帶Fe-S礦物的形成和累積，亟需加強(qiáng)該方面探討，以更好規(guī)劃該問題土壤。該方面應(yīng)進(jìn)一步探討ASS發(fā)育過程中不同來源、 形態(tài)的黃鐵礦對土壤各種理化性狀的影響。

2) ASS的形成及發(fā)育過程中，F(xiàn)e-S礦物的轉(zhuǎn)化顯著影響著其他金屬元素的固定、 活化、 溶解等一系列地球化學(xué)過程。其中黃鐵礦形成過程中重金屬的富集、 黃鐵礦氧化過程中重金屬的活化是國內(nèi)外研究熱點(diǎn)。近些年，國外有學(xué)者開始關(guān)注ASS對稀土元素、 痕量元素的影響，但國內(nèi)尚無相關(guān)報(bào)道。

3) 盡管我國ASS的面積高達(dá)0.11 M hm2，但是從學(xué)術(shù)界到社會(huì)上，對其了解、 認(rèn)識仍處于表面的危害性。曾有部分學(xué)者進(jìn)行過探討，但均沒有深入到機(jī)理層面上，而社會(huì)上對該類土壤概念模糊，只注重其生產(chǎn)應(yīng)用，忽視了其潛在的環(huán)境危害、 及產(chǎn)品安全性的考量。在我國大量的ASS被改造成水稻田，采用適當(dāng)?shù)母牧肌?排水措施能保證相當(dāng)?shù)漠a(chǎn)量收成，被認(rèn)為是ASS利用的有效途徑。然而，ASS開墾種稻后，相應(yīng)的農(nóng)藝措施對土壤酸、 重金屬的影響如何，其對周邊河流、 環(huán)境、 居民的影響如何，甚至稻谷的安全性均有待進(jìn)一步評估。

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