• ISSN 1008-505X
  • CN 11-3996/S

不同有机酸对石灰性土壤磷的活化效应及机理

Low molecular weight organic acids activate insoluble soil P through competition adsorption sites and chelating reaction in calcareous soils

  • 摘要:
    目的 添加低分子量有机酸是活化土壤难溶性磷有效途径。比较研究几种低分子量有机酸及其组合对土壤磷的活化性能,为土壤磷的高效利用提供依据。
    方法 低磷和高磷石灰性土壤选自新疆石河子,设置5个低分子有机酸添加处理:草酸、柠檬酸、黄腐酸、柠檬酸+草酸、草酸+柠檬酸+黄腐酸处理,和一个0.01 mmol/L KCl对照。采用吸附平衡实验法测定土壤磷的吸附量;采用土壤吸附动力学实验法测定土壤磷的解吸动力学。采用常规和灭菌土壤培养方法,通过连续浸提法研究低分子有机酸及其组合对磷组分动态转化的影响和pH对磷的活化效应。
    结果 Langmuir与Elovich模型均可较好地拟合土壤对磷的吸附热力学 (R2 = 0.852~0.994) 与吸附动力学过程 (R2 = 0.882~0.975)。低磷土壤的最大吸附量 (Qmax)、最大缓冲容量 (MBC)、吸附力常数 (KL) 和吸附速率 (b) 均高于高磷土壤,表明低磷土壤对磷的吸附更强。低分子量有机酸添加均降低了QmaxMBCb。草酸对QmaxMBC的降幅最大,低磷土壤降幅分别为28.5%和74.9%,高磷土壤分别为14.7%和73.3%。柠檬酸对低磷土壤的b值降幅最大 (80.9%),草酸对高磷土壤的b值降幅最大 (22.0%)。与CK相比,草酸添加显著提高了Olsen-P含量,草酸+柠檬酸效果次之,黄腐酸对磷的活化效果最差。不灭菌培养条件下,草酸和草酸+柠檬酸处理低磷土壤的Olsen-P含量分别增加了 42.6%和18.5%,高磷土壤分别增加了27.3%和1.01%;草酸和草酸+柠檬酸处理的活性磷组分Resin-P在低磷土壤中分别增加了80.9%和77.4%,在高磷土壤中分别增加了79.5%和72.8%;非活性磷组分Di HCl-P在低磷土壤中分别降低了8.87%和5.89% ,在高磷土壤中分别降低了8.83%和5.54%;Con HCl-P在低磷土壤中分别降低了25.1%和12.9%,在高磷土壤中分别降低了16.9%和5.30%。柠檬酸处理的Resin-P在低磷和高磷土壤中分别增加了70.2%和79.5%,而NaOH-P则分别降低了14.8%、26.3%,说明草酸、草酸+柠檬酸促进了非活性磷向活性磷组分的转化,柠檬酸则促进了中活性磷向活性磷组分的转化。土壤灭菌培养各处理磷组分含量与不灭菌培养无显著差异,说明微生物对有机酸活化土壤磷的效应无显著影响。不论是否灭菌,土壤Olsen-P含量的增加与pH降低呈负相关,因此致酸效应不是小分子有机酸活化土壤难溶性磷的主要机制。
    结论 小分子有机酸通过与磷竞争吸附位点或进行螯合反应活化土壤磷,而不是通过致酸效应或激发磷活化相关的微生物。3种小分子有机酸相比,草酸活化磷的效果最大,其次是柠檬酸、黄腐酸,单一有机酸的活化效果大于有机酸组合。

     

    Abstract:
    Objectives Low molecular weight organic acids (LMWOAs) have been noticed effective in mobilizing soil insoluble phosphorus (P). We compared the activating effects of LMWOAs, the possible mechanisms and the proper way of application.
    Methods The LMWOAs used in the research included oxalic acid (OA), citric acid (CA), fulvic acid (FA), oxalic acid plus citric acid (OA + CA), and the three acids together (OA + CA + FA), and KCl was used as control. The low- and high-P soils were collected from Shihezi City, Xinjiang. The P adsorption amount of soils was tested by adsorption balance experiment. The adsorption dynamics of P was tested by isotherm adsorption experiment. The P was fractioned by continuous extraction method and the pH was measured after the unsterilized and sterilized soils were incubated for 30 days.
    Results Langmuir and Elovich equation well fitted soil P adsorptive thermodynamics (R2 = 0.852−0.994) and adsorptive dynamics processes (R2 = 0.882−0.975) either in low- or high-P soil. The maximum P adsorption (Qmax), maximum buffer capacity (MBC), Langmuir coefficient (KL) and Elovich constant (b) in low-P soil were significantly higher than those in high-P soil, indicating the stronger P adsorption capacity of low-P soil. All the OA, CA, and FA addition notably decreased Qmax, MBC and b values. OA resulted in the largest decrease in Qmax and MBC values, with decrease by 28.5% and 74.9% in low-P soil, and by 14.7% and 73.3% in high-P soil. CA resulted in significant decrease of b value in low-P soil (80.9%), while OA did that by 22.0% in the high-P soil. Compared to CK, the highest Olsen-P content was exhibited in OA treated soil, followed in OA+CA soil, the least effect was in FA treated soil. Under unsterilized condition, OA and OA+CA significantly increased soil Olsen-P by 42.6% and 18.5% in low-P soil, and by 27.3% and 1.01% in high-P soil; increased Resin-P by 80.9% and 77.4% in low-P soil, and 79.5% and 72.8% in high-P soil; decreased Di HCl-P by 8.87% and 5.89% in low-P soil, and 8.83% and 5.54% in high-P soil; decreased Con HCl-P by 25.1% and 12.9% in low-P soil and by 16.9% and 5.30% in high-P soil. CA increased Resin-P by 70.2% and 79.5% in low- and high-P soil, but decreased NaOH-Pi by 14.8% and 26.3%, accordingly, suggesting that OA and OA+CA facilitated soil P transformation from non-labile to labile P fractions, while CA favored to the transformation of NaOH-P to Resin-P. FA did not show significant P mobilizing effect. Besides, the sterilized and unsterilized soils were tested with similar P fraction contents, suggesting not important P-solubilizing effect by microorganisms. The Olsen-P increase was negatively correlated to the decrease of soil pH, implying the negligible effect induced by acidification due to the addition of low molecular organic acids.
    Conclusions Low molecular organic acids could increase soil P bioavailability in calcareous soils mainly through competition on the adsorption sites and chelation reaction with soil P, rather than acidification and microbiological mechanism. The mobilizing efficiency of soil P is in order of oxalic acid > citric acid > fulvic acid, and the single application is more effective than the combined application in mobilizing soil P.

     

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