长期定位施肥对棕壤钾素供应特征及有效性影响
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摘要
本文以沈阳农业大学棕壤肥料长期定位试验研究为平台，研究了玉米-玉米-大豆轮作种植条件下，长期不同施肥模式对棕壤钾素供应能力的影响及棕壤钾形态的时空变异特征；探讨了不同施肥处理对粘土矿物组成及含钾矿物间转化的影响；棕壤钾素的固定特征、钾素吸附解吸动力学特征及棕壤钾素Q/I特征，以期为提高钾肥利用效率，合理施用钾肥提供理论依据。主要研究结果如下：
1、长期不同施肥影响棕壤供钾能力及钾素有效性。不施钾、单施化学钾肥或单施低量有机肥土壤钾素长期供应能力及有效性都降低。长期单施高量有机肥（M2）可以提高土壤钾素的有效性，但不能维持其长期供应能力。施用高量有机肥配合化学钾肥（M2NPK）处理长期供应能力强，钾素有效性高。
2、从土壤钾不同吸附点位（p位、e位和i位）的角度开展对长期不同施肥对钾矿物固定点位钾的时空变异研究。结果表明：长期单施高量有机肥可以维持土壤p位、e位和i位钾含量，有机肥配合化学钾肥施用提高p位、e位和i位钾含量。p位、e位和i位钾含量的垂直分布表现为0~20cm高于20~40cm。
3、X射线衍射鉴定结果表明：长期不同施肥处理棕壤粘土矿物（＜2μm）种类没有发生变化，不同处理矿物组成相同（水云母、高岭石、绿泥石、蛭石、蒙脱石及少量的石英）；施钾和有机肥影响粘土矿物中水云母的含量：单施高量有机肥或配合化学钾肥处理土壤中水云母含量增加，长期不施钾肥处理水云含量显著下降；水云母与蛭石-绿泥石相互转化，互为消长，相关分析表明：水云母含量与蛭石-绿泥石呈显著负相关关系（r=0.859，P=0.028）；速效钾和缓效钾与粘土矿物变化关系密切：缓效性钾和速效钾与水云母呈正相关关系（0.908*和0.947**），而与蛭石-绿泥石呈负相关关系（-0.958**和0.921**）。
4、对连续32年不同施肥处理棕壤钾素的固钾量分析表明，当外源钾浓度在400~4000mg·kg-1范围时，随浓度增加固钾量升高，固钾率随浓度增加而降低。与不施钾相比，施钾和有机肥降低了土壤固钾能力；土壤基本理化性质与固钾量关系密切，相关分析表明：有机质与固钾量呈极显著负相关；粘粒（＜2μm）与固钾量呈显著负相关；速效钾与固钾量呈极显著负相关；缓效钾与固钾量呈极显著负相关；阳离子交换量与固钾量呈负相关关系，但未达到显著性水平。
5、采用去离子水淋洗土壤，连续液流法研究耕层土壤钾素的吸附解吸动力学。结果表明，各处理土壤到达吸附解吸的平衡时间和平衡量各不相同。且平衡解吸时间比平衡吸附时间长，平衡吸附量比平衡解吸量大；反应速度与反应时间关系符合方程V=A+Blnt，且线性关系良好；长期不同施肥土壤理化性质的改变对棕壤钾素吸附解吸动力学特征产生一定影响：CEC、粘粒、有机质、速效钾与吸附解吸各参数呈现不同程度的相关性；一级动力学方程对吸附解吸过程适用性最好，说明经去离子水预处理，在连续液流情况下，长期施肥棕壤K+吸附解吸动力学的主要控制过程是膜扩散过程。
6、经过32年不同施肥棕壤钾素Q/I曲线形状基本相同。不同处理Q/I特征参数（-ΔK~0、AR_e~K、PBC~K和K_X）差异较大：长期施钾肥和有机肥可以提高土壤-ΔK~0值，增加专性吸附位点钾素的含量（K_X），有机肥对K_X的影响强于对-ΔK~0的影响；长期施钾肥和有机肥处理土壤易释放钾有效性较高，M_2NPK和M_2处理吸附的钾主要保持在晶格边缘，其他各处理吸附的钾主要保持在粘土矿物晶格层间；长期施钾肥和有机肥土壤PBC~K值降低。长期施肥土壤理化性质影响钾素Q/I曲线特征参数；通径分析表明：粘粒含量通过间接作用影响-ΔK~0；有机质间接影响PBC~K值；速效钾含量直接关系到AR_e~K值的变化，速效钾对K_X值有强烈的直接作用，这种作用是通过有机质、粘粒含量及阳离子交换量对速效钾的间接作用产生的。
综上所述，长期不同施肥影响棕壤供钾能力及钾素的有效性，其中高量有机肥配合化学钾肥是保持土壤供钾能力和有效性的最优施肥模式，因此在农业生产中注意有机物料投入的同时，还应注意化学钾肥的搭配施用。钾在土壤中化学行为复杂，受到多种因素的制约，研究表明长期定位施肥条件下土壤理化性质的改变是影响钾素供应能力及有效性的重要原因之一。
This study based on a long-term fertilizer location experiment of brown soils inShenyang Agricultural University concentrates on the research of effect of differentfertilization on potassium supply capacity, spatial-temporal variation characteristics of Kadsorbed by minerals, transformation between potassium mineral, features of fixation,adsorption and desorption dynamics, Q/I value of potassium in brown soils. The objectives ofthis study are providing theoretical foundation of rational application of potassic fertilizeralong with improving fertilizer availability ratio. Some results as follows:
1. Long-term different fertilization affects potassium supplying power and effectivenessof potassium. The results show that long-term no-potassic fertilizer, single potassic fertilizer,and single low level of organic fertilizer treatments reduce the soil K deliverability andeffectiveness. Long-term single high level of organic fertilizer treatment (M2) could improvesoil K effectiveness, but it is unable to maintain long-term supply capacity of soil K.Combined application of high level of organic fertilizer and potassic fertilizer can improvesupply capacity and effectiveness of soil K.
2. Study of temporal and spatial variation of potassium mineral fixation in different soilpotassium adsorption points(p, e and i sites) in the condition of long-term differentfertilization shows that (1) both long-term single high level of organic fertilizer and combinedapplication of organic fertilizer and potassic fertilizer could maintain the soil absorbedpotassium content of p, e and i sites;(2) spatial variability of the soil absorbed potassiumcontent of p, e and i sites displays that0~20cm＞20~40cm.
3. The result of X-ray diffraction identification shows that (1) there is no change inrespect of species of clay mineral (＜2μm) and mineral composition (hydromica, chlorite,kaolinite, montmorillonite, vermiculite and small amounts of quartz) under long-termdifferent fertilization;(2) application of both potassic fertilizer and organic fertilizer affect thecontent of hydromica in clay mineral, and single high level of organic fertilizer or combinedwith potassic fertilizer could increase the content of hydromica. However no-potassicfertilizer application makes the content of hydromica decline significantly. There is mutualtransformation between hydromica and vermiculite-chlorite. The correlation analysis shows that there is a significant negative correlation between the content of hydromica andvermiculite-chlorite (r=0.859, P=0.028), and S-avail K and R-avail K have close relationswith the change of clay mineral: there are positive correlations between the content ofhydromica and S-avail K and R-avail K (0.908*and0.947**). Nevertheless there arenegative correlations between the content of vermiculite-chlorite and S-avail K and R-avail K(-0.958**and-0.921**).
4. Analysis of potassium fixation capacity of brown soils in the condition of32consecutive years fertilization shows that (1) when the concentration of exogenous potassiumis in range of400~4000mg·kg~(-1), potassium fixation capacity increases along with the rise ofconcentration of exogenous potassium, whereas K fixation rate reduces;(2) compared withno-potassic fertilizer, application of potassic fertilizer and organic fertilizer reduces soilpotassium fixation capacity;(3) there are close relations between physio-chemical propertiesand potassium fixation capacity of soil. The correlation analysis shows that (1) there issignificantly negative correlation between R-avail K and potassium fixation capacity;(2)there are significant negative correlations between potassium fixation capacity, R-avail K,S-avail K and clay particle (＜2μm);(3) there is negative correlation between CEC andpotassium fixation capacity.
5. Samples of arable layer were flowed through with deionized water as pretreatment toinvestigate the kinetics characteristics of K+adsorption and desorption of brown soil underlong-term (32years) fertilization. Result shows that (1) the equilibrium time and amount ofadsorption and desorption were different, and the time of desorption is longer than adsorption,amount is inverse. The changes of the velocity of potassium adsorbing and desorbing with theincreasing time can be described by the model of V=A+Blnt. There were correlation betweenparameters of adsorption and desorption were related with CEC、Clay、OM and R-avail K indifferent degree. First-order, Elovich, parabolic diffusion and dual constant were used todescribe the kinetics of K adsorption and desorption of experimental soils. The result showedthat first-order was the best of the various kinetic equations.The effect of long-termfertilization on K+adsorption and desorption kinetics of brown soil is up to the changes ofphysic-chemical properties of soil. Under this experiment condition, the K+adsorption and desorption kinetics is mainly controlled by surface diffusion
6. Potassium Q/I curve shape of brown soils is basically the same after32years ofdifferent fertilization.Characteristic parameters of Q/I of different treatments（-ΔK~0、AR_e~K、PBC~K和K_X） have large differences. Long-term application of potassic fertilizer and organicfertilizer could improve-ΔK~0value and K content of specific adsorption sites(K_X),andorganic fertilizer affects K_Xmore than-ΔK~0.Long-term application of potassic fertilizer andorganic fertilizer makes the effectiveness of soil K higher. Absorbed potassium of M_2NPKand M_2mainly stay in the lattice edge, however that of other treatments mainly keeps in theinterlayer of crystal lattice of clay minerals. Long-term application of potassic fertilizer andorganic fertilizer makes the value of soil PBC~Klower. The physicochemical properties of soilaffect potassium Q/I curve parameters. Path analysis shows that (1) the content of clay affects-ΔK~0indirectly, and organic matter affects PBC~Kindirectly;(2) rapidly available potassiumaffects AR_e~Kand K_Xdirectly,which is through the organic matter, clay content and cationexchange capacity of soil that affect rapidly available potassium indirectly.
To sum up, long-term different fertilization affects potassium supplying capacity andeffectiveness of potassium of brown soils, in which combined application of high level oforganic fertilizer and potassic fertilizer is the optimum fertilization model of maintain soilpotassium supplying capacity and effectiveness of potassium. Therefore more attentionshould be payed to using potassic fertilizer combined with organic fertilizer in agriculturalproduction. Chemical behavior of potassium is complex in soils, and is restricted by manykinds of factors. This study shows that the effect of long-term different fertilization on soilpotassium supplying capacity and effectiveness is by way of changing physio-chemicalproperties of soil.
1、长期不同施肥影响棕壤供钾能力及钾素有效性。不施钾、单施化学钾肥或单施低量有机肥土壤钾素长期供应能力及有效性都降低。长期单施高量有机肥（M2）可以提高土壤钾素的有效性，但不能维持其长期供应能力。施用高量有机肥配合化学钾肥（M2NPK）处理长期供应能力强，钾素有效性高。
2、从土壤钾不同吸附点位（p位、e位和i位）的角度开展对长期不同施肥对钾矿物固定点位钾的时空变异研究。结果表明：长期单施高量有机肥可以维持土壤p位、e位和i位钾含量，有机肥配合化学钾肥施用提高p位、e位和i位钾含量。p位、e位和i位钾含量的垂直分布表现为0~20cm高于20~40cm。
3、X射线衍射鉴定结果表明：长期不同施肥处理棕壤粘土矿物（＜2μm）种类没有发生变化，不同处理矿物组成相同（水云母、高岭石、绿泥石、蛭石、蒙脱石及少量的石英）；施钾和有机肥影响粘土矿物中水云母的含量：单施高量有机肥或配合化学钾肥处理土壤中水云母含量增加，长期不施钾肥处理水云含量显著下降；水云母与蛭石-绿泥石相互转化，互为消长，相关分析表明：水云母含量与蛭石-绿泥石呈显著负相关关系（r=0.859，P=0.028）；速效钾和缓效钾与粘土矿物变化关系密切：缓效性钾和速效钾与水云母呈正相关关系（0.908*和0.947**），而与蛭石-绿泥石呈负相关关系（-0.958**和0.921**）。
4、对连续32年不同施肥处理棕壤钾素的固钾量分析表明，当外源钾浓度在400~4000mg·kg-1范围时，随浓度增加固钾量升高，固钾率随浓度增加而降低。与不施钾相比，施钾和有机肥降低了土壤固钾能力；土壤基本理化性质与固钾量关系密切，相关分析表明：有机质与固钾量呈极显著负相关；粘粒（＜2μm）与固钾量呈显著负相关；速效钾与固钾量呈极显著负相关；缓效钾与固钾量呈极显著负相关；阳离子交换量与固钾量呈负相关关系，但未达到显著性水平。
5、采用去离子水淋洗土壤，连续液流法研究耕层土壤钾素的吸附解吸动力学。结果表明，各处理土壤到达吸附解吸的平衡时间和平衡量各不相同。且平衡解吸时间比平衡吸附时间长，平衡吸附量比平衡解吸量大；反应速度与反应时间关系符合方程V=A+Blnt，且线性关系良好；长期不同施肥土壤理化性质的改变对棕壤钾素吸附解吸动力学特征产生一定影响：CEC、粘粒、有机质、速效钾与吸附解吸各参数呈现不同程度的相关性；一级动力学方程对吸附解吸过程适用性最好，说明经去离子水预处理，在连续液流情况下，长期施肥棕壤K+吸附解吸动力学的主要控制过程是膜扩散过程。
6、经过32年不同施肥棕壤钾素Q/I曲线形状基本相同。不同处理Q/I特征参数（-ΔK~0、AR_e~K、PBC~K和K_X）差异较大：长期施钾肥和有机肥可以提高土壤-ΔK~0值，增加专性吸附位点钾素的含量（K_X），有机肥对K_X的影响强于对-ΔK~0的影响；长期施钾肥和有机肥处理土壤易释放钾有效性较高，M_2NPK和M_2处理吸附的钾主要保持在晶格边缘，其他各处理吸附的钾主要保持在粘土矿物晶格层间；长期施钾肥和有机肥土壤PBC~K值降低。长期施肥土壤理化性质影响钾素Q/I曲线特征参数；通径分析表明：粘粒含量通过间接作用影响-ΔK~0；有机质间接影响PBC~K值；速效钾含量直接关系到AR_e~K值的变化，速效钾对K_X值有强烈的直接作用，这种作用是通过有机质、粘粒含量及阳离子交换量对速效钾的间接作用产生的。
综上所述，长期不同施肥影响棕壤供钾能力及钾素的有效性，其中高量有机肥配合化学钾肥是保持土壤供钾能力和有效性的最优施肥模式，因此在农业生产中注意有机物料投入的同时，还应注意化学钾肥的搭配施用。钾在土壤中化学行为复杂，受到多种因素的制约，研究表明长期定位施肥条件下土壤理化性质的改变是影响钾素供应能力及有效性的重要原因之一。
This study based on a long-term fertilizer location experiment of brown soils inShenyang Agricultural University concentrates on the research of effect of differentfertilization on potassium supply capacity, spatial-temporal variation characteristics of Kadsorbed by minerals, transformation between potassium mineral, features of fixation,adsorption and desorption dynamics, Q/I value of potassium in brown soils. The objectives ofthis study are providing theoretical foundation of rational application of potassic fertilizeralong with improving fertilizer availability ratio. Some results as follows:
1. Long-term different fertilization affects potassium supplying power and effectivenessof potassium. The results show that long-term no-potassic fertilizer, single potassic fertilizer,and single low level of organic fertilizer treatments reduce the soil K deliverability andeffectiveness. Long-term single high level of organic fertilizer treatment (M2) could improvesoil K effectiveness, but it is unable to maintain long-term supply capacity of soil K.Combined application of high level of organic fertilizer and potassic fertilizer can improvesupply capacity and effectiveness of soil K.
2. Study of temporal and spatial variation of potassium mineral fixation in different soilpotassium adsorption points(p, e and i sites) in the condition of long-term differentfertilization shows that (1) both long-term single high level of organic fertilizer and combinedapplication of organic fertilizer and potassic fertilizer could maintain the soil absorbedpotassium content of p, e and i sites;(2) spatial variability of the soil absorbed potassiumcontent of p, e and i sites displays that0~20cm＞20~40cm.
3. The result of X-ray diffraction identification shows that (1) there is no change inrespect of species of clay mineral (＜2μm) and mineral composition (hydromica, chlorite,kaolinite, montmorillonite, vermiculite and small amounts of quartz) under long-termdifferent fertilization;(2) application of both potassic fertilizer and organic fertilizer affect thecontent of hydromica in clay mineral, and single high level of organic fertilizer or combinedwith potassic fertilizer could increase the content of hydromica. However no-potassicfertilizer application makes the content of hydromica decline significantly. There is mutualtransformation between hydromica and vermiculite-chlorite. The correlation analysis shows that there is a significant negative correlation between the content of hydromica andvermiculite-chlorite (r=0.859, P=0.028), and S-avail K and R-avail K have close relationswith the change of clay mineral: there are positive correlations between the content ofhydromica and S-avail K and R-avail K (0.908*and0.947**). Nevertheless there arenegative correlations between the content of vermiculite-chlorite and S-avail K and R-avail K(-0.958**and-0.921**).
4. Analysis of potassium fixation capacity of brown soils in the condition of32consecutive years fertilization shows that (1) when the concentration of exogenous potassiumis in range of400~4000mg·kg~(-1), potassium fixation capacity increases along with the rise ofconcentration of exogenous potassium, whereas K fixation rate reduces;(2) compared withno-potassic fertilizer, application of potassic fertilizer and organic fertilizer reduces soilpotassium fixation capacity;(3) there are close relations between physio-chemical propertiesand potassium fixation capacity of soil. The correlation analysis shows that (1) there issignificantly negative correlation between R-avail K and potassium fixation capacity;(2)there are significant negative correlations between potassium fixation capacity, R-avail K,S-avail K and clay particle (＜2μm);(3) there is negative correlation between CEC andpotassium fixation capacity.
5. Samples of arable layer were flowed through with deionized water as pretreatment toinvestigate the kinetics characteristics of K+adsorption and desorption of brown soil underlong-term (32years) fertilization. Result shows that (1) the equilibrium time and amount ofadsorption and desorption were different, and the time of desorption is longer than adsorption,amount is inverse. The changes of the velocity of potassium adsorbing and desorbing with theincreasing time can be described by the model of V=A+Blnt. There were correlation betweenparameters of adsorption and desorption were related with CEC、Clay、OM and R-avail K indifferent degree. First-order, Elovich, parabolic diffusion and dual constant were used todescribe the kinetics of K adsorption and desorption of experimental soils. The result showedthat first-order was the best of the various kinetic equations.The effect of long-termfertilization on K+adsorption and desorption kinetics of brown soil is up to the changes ofphysic-chemical properties of soil. Under this experiment condition, the K+adsorption and desorption kinetics is mainly controlled by surface diffusion
6. Potassium Q/I curve shape of brown soils is basically the same after32years ofdifferent fertilization.Characteristic parameters of Q/I of different treatments（-ΔK~0、AR_e~K、PBC~K和K_X） have large differences. Long-term application of potassic fertilizer and organicfertilizer could improve-ΔK~0value and K content of specific adsorption sites(K_X),andorganic fertilizer affects K_Xmore than-ΔK~0.Long-term application of potassic fertilizer andorganic fertilizer makes the effectiveness of soil K higher. Absorbed potassium of M_2NPKand M_2mainly stay in the lattice edge, however that of other treatments mainly keeps in theinterlayer of crystal lattice of clay minerals. Long-term application of potassic fertilizer andorganic fertilizer makes the value of soil PBC~Klower. The physicochemical properties of soilaffect potassium Q/I curve parameters. Path analysis shows that (1) the content of clay affects-ΔK~0indirectly, and organic matter affects PBC~Kindirectly;(2) rapidly available potassiumaffects AR_e~Kand K_Xdirectly,which is through the organic matter, clay content and cationexchange capacity of soil that affect rapidly available potassium indirectly.
To sum up, long-term different fertilization affects potassium supplying capacity andeffectiveness of potassium of brown soils, in which combined application of high level oforganic fertilizer and potassic fertilizer is the optimum fertilization model of maintain soilpotassium supplying capacity and effectiveness of potassium. Therefore more attentionshould be payed to using potassic fertilizer combined with organic fertilizer in agriculturalproduction. Chemical behavior of potassium is complex in soils, and is restricted by manykinds of factors. This study shows that the effect of long-term different fertilization on soilpotassium supplying capacity and effectiveness is by way of changing physio-chemicalproperties of soil.
引文
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