外源低分子有机酸对东北黑土有效磷的活化性能与机制研究

Activation Performance and Mechanisms of Exogenous Low-Molecular-Weight Organic Acids toward Available Phosphorus in Black Soils of Northeast China

  • 摘要: 中国东北黑土区长期过量施用磷肥,造成土壤磷素累积、有效性下降,活化土壤有效磷(Available Phosphorus,AP)对农业可持续发展具有重要意义。已有研究表明,低分子有机酸是高效磷活化剂,其中草酸与柠檬酸效果突出,作用机制以酸溶解、络合与竞争吸附协同为主。但针对东北黑土这类非石灰性土壤,系统对比多种有机酸对磷形态动态转化影响的研究尚显不足。为此,本文选取草酸、柠檬酸、苹果酸、抗坏血酸4种低分子有机酸,通过室内培养试验,探究0% ~ 2%浓度处理对暗棕壤与典型黑土有效磷的活化效果与机制。采用Hedley连续提取法分级提取各磷形态磷,以电感耦合等离子体发射光谱法(ICP-OES)测定含量,结合冗余分析(RDA)揭示磷组分与环境因子的关系。结果表明:①添加有机酸可显著提升土壤有效磷,在第20 d左右达峰值后趋于稳定,提升效果随浓度升高而增强,2%处理最为显著。②草酸与柠檬酸活化能力最强,2%处理使两种土壤有效磷最高分别提升143.9%和120.1%,与二者显著提升非石灰性土壤有机磷活化效果的已有结论一致。③不同有机酸活化路径存在差异:草酸主要活化钙结合态磷(HCl-P);柠檬酸可同步转化中稳性有机磷(NaOH-Po)与HCl-P;苹果酸主要影响铁铝结合态无机磷(NaOH-Pi);抗坏血酸可活化残渣态磷(Res-P)。RDA分析证实,东北黑土虽属非石灰性土壤,但因其高钙质(HCl-P占比19.0%)与高有机质特征,磷的活化过程以钙络合为主导。土壤pH与溶解性有机碳(DOC)是驱动磷形态转化的核心环境因子。该土壤的活化路径以HCl-P的酸解与络合为主,显著区别于普通酸性非石灰性土壤中以铁铝结合态磷为主的机制,体现了非石灰性土壤因基质差异而产生的活化机制分异。草酸和柠檬酸通过酸解、配位交换与有机磷矿化协同作用,可有效提升黑土磷有效性,为黑土区磷肥合理调控提供依据。

     

    Abstract: In the black soil region of Northeast China, long-term excessive application of phosphorus fertilizers has led to soil phosphorus accumulation and reduced availability. Activating soil available phosphorus (AP) is therefore crucial for sustainable agricultural development. Previous studies have shown that low-molecular-weight organic acids are effective phosphorus activators, with oxalic and citric acids exhibiting particularly significant effects. Their mechanisms involve the synergy of acid dissolution, complexation, and competitive adsorption. However, systematic studies are still lacking regarding the comparative effects of various organic acids on the dynamic transformation of phosphorus forms in the black soils of Northeast China, which are non-calcareous. To address this gap, this study selected four low-molecular-weight organic acids-oxalic, citric, malic, and ascorbic acids and conducted an incubation experiment. The experiment aimed to investigate the activation performance and mechanisms of these acids at different concentrations (0% to 2%) on available phosphorus in both dark brown soil and typical black soil. We employed the Hedley sequential extraction procedure to fractionate soil phosphorus. The phosphorus content in each fraction was determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) to analyze its dynamic changes. Redundancy analysis (RDA) was used to elucidate the relationships between phosphorus fractions and soil environmental factors. The results showed that: (1) The addition of organic acids significantly increased soil AP content, which peaked around day 20 of incubation and then gradually stabilized. The enhancement effect strengthened with increasing concentration, with the 2% treatment being the most pronounced. (2) Oxalic and citric acids exhibited the strongest activation capacity. Their 2% treatments maximally increased AP content in the two soils by 143.9% and 120.1%, respectively. This is consistent with the existing conclusions that both have significantly enhanced the activation effect of organic phosphorus in non-limestone soils. (3) Analysis of phosphorus transformation revealed distinct activation pathways: oxalic acid primarily decreased calcium-bound phosphorus (HCl-P); citric acid concurrently promoted the transformation of moderately stable organic phosphorus (NaOH-Po) and HCl-P; malic acid mainly affected iron/aluminum-bound inorganic phosphorus (NaOH-Pi); whereas ascorbic acid activated residual phosphorus (Res-P). RDA confirmed that despite being non-calcareous, the black soils exhibited high calcium content (HCl-P accounted for 19.0%) and high organic matter. Consequently, phosphorus activation was predominantly governed by calcium complexation, with soil pH and dissolved organic carbon (DOC) identified as the key environmental factors driving phosphorus form transformation. The activation pathway primarily focused on the acidolysis and complexation of calcium-bound phosphorus (HCl-P), diverging significantly from the mechanism in typical acidic non-calcareous soils, which is dominated by the release of iron/aluminum-bound phosphorus. This highlights the differences in activation mechanisms among non-calcareous soils due to varying substrate properties. In Northeast China’s black soils, oxalic and citric acids hold an advantage in enhancing phosphorus availability through the combined effects of acidolysis, ligand exchange, and the promotion of organic phosphorus mineralization. This insight provides a basis for the rational regulation of phosphate fertilizer use in the black soil region.

     

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