低分子有机酸对滨海盐化潮土磷吸附解吸特性和磷形态的影响

Effects of low-molecular-weight organic acids on phosphorus adsorption-desorption characteristics and phosphorus fractions in coastal saline soil

  • 摘要: 环渤海滨海盐碱地富含碳酸钙等石灰质成分, pH>8, 土壤磷素极易被吸附或转化为难溶的磷酸钙盐。低分子有机酸是植物和微生物的重要活磷策略, 其中草酸和柠檬酸的磷活化效果最好, 且在土壤中广泛存在, 但关于它们在滨海盐碱地中作用机理的研究较少。因此, 本研究采用批量试验法和改进的Hedley磷素分级法, 探究了5 (C5)、10 (C10)、50 (C50) mmol∙kg−1草酸和5 (N5)、10 (N10)、50 (N50) mmol∙kg−1柠檬酸对滨海盐化潮土磷素吸附解吸特性和形态转化的影响。结果表明: 1)草酸抑制磷素吸附和活化磷素的能力比柠檬酸强。草酸和柠檬酸均可通过—COO与磷酸盐竞争结合位点, 促进磷素的解吸与活化, 草酸以阴离子作用为主, 柠檬酸以质子酸作用为主。2) C50在30 d内促进了土壤稳定性无机磷(Pi)向活性Pi的转化。但N50的活化机制与以往研究不同, 在短期培养(3 d)土壤中促进了活性Pi和稳定性Pi向中活性Pi的转化, 使中活性Pi显著提高1.33%。各处理均有促进中活性有机磷(Po)向活性Po转化的趋势。3) C10、C50和N50可以提高土壤有效磷含量。但低分子有机酸存在时效性, 在第3天解磷效果开始降低, 柠檬酸第10天完全失效, 草酸第30天仍有效。4)土壤对磷素的吸附解吸能力与稀HCl提取态Pi (D.HCl-Pi)显著相关, 磷素形态中NaHCO3提取态Pi (NaHCO3-Pi)与D.HCl-Pi显著负相关, D.HCl-Pi是影响滨海盐化潮土磷素有效性的关键磷素形态。基于研究结果, 建议环渤海滨海盐碱地中施用10~50 mmol∙kg−1草酸, 可显著且持久地提高土壤磷活性。

     

    Abstract: In the coastal saline-alkali soils of the Bohai Rim region, the abundance of calcareous components (e.g., calcium carbonate) and high pH (>8) lead to strong phosphorus adsorption and rapid conversion into insoluble calcium phosphate salts. Low-molecular-weight organic acids (LMWOAs), particularly oxalic and citric acids, are known for their superior phosphorus-solubilizing capacity and ubiquitous presence in soils, and play a crucial role in phosphorus mobilization for plants and microorganisms. However, their mechanisms in coastal saline-alkali soils are not yet fully understood. Consequently, this study used batch experiments and a modified Hedley phosphorus classification method to investigate the effects of different concentrations of oxalic acid (C5: 5 mmol∙kg−1, C10: 10 mmol∙kg−1, C50: 50 mmol∙kg−1) and citric acid (N5: 5 mmol∙kg−1, N10: 10 mmol∙kg−1, N50: 50 mmol∙kg−1) on the adsorption-desorption characteristics and transformation of phosphorus fractions in coastal saline soils. Oxalic acid demonstrated a stronger ability to inhibit phosphorus adsorption and activate phosphorus than citric acid. Both oxalic and citric acids promoted phosphorus desorption and activation by competing for binding sites with phosphate ions via —COO. Oxalic acid primarily functions through anion effects, while citric acid mainly acts via hydrogen ion (the “proton”) effects. C50 promoted the transformation of stable inorganic phosphorus (Pi) to labile Pi in the soil within 30 days. However, the activation mechanism of N50 differed from those reported in previous studies. During short-term incubation (3 days), N50 promoted the transformation of labile Pi and stable Pi into moderately labile Pi, resulting in a significant increase of 1.33% in moderately labile Pi. All the treatments promoted the transformation of moderately labile Po to labile Po. The C10, C50, and N50 treatments increased the available phosphorus in the soil. However, the effectiveness of the low-molecular-weight organic acids showed a time-dependent pattern. In saline-alkali soils, the effects began to diminish after 3 days, with citric acid losing its effectiveness completely by day 10, whereas oxalic acid remained effective until day 30. Soil adsorption and desorption capacities of phosphorus significantly correlated with diluted HCl-extracted Pi (D. HCl-Pi). On phosphorus fractions, NaHCO3-extracted Pi (NaHCO3-Pi) negatively correlated with D. HCl-Pi. D. HCl-Pi is the key phosphorus fraction governing phosphorus availability in coastal saline soils. According to the study results, applying 10–50 mmol∙kg−1 oxalic acid is recommended for Bohai Rim coastal saline-alkali soils, which can significantly and persistently enhance soil phosphorus availability.

     

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