长期施肥条件下土壤微量元素化学特性及有效性研究
发布时间：2018-07-13 20:45
【摘要】：土壤中微量元素的有效性研究已成为农业和环境科学领域关注的焦点。施肥是微量元素进入土壤的一个重要途径,明确和揭示施肥与土壤微量元素有效性之间的关系可为农业生产实践提供科学参考依据。本文研究了长期施肥条件下土壤微量元素含量、形态、分布特征及其变化情况,分析了影响土壤微量元素有效性的因素,探讨了土壤微量元素有效性变化产生的机制,所取得的主要结论如下:(1)长期种植作物和施肥均降低了土壤pH值和碳酸钙含量,增加了土壤有机质含量。2015年苜蓿连作耕层土壤pH值降低最多,较裸地相比降低了0.44个pH单位。粮豆轮作系统中耕层土壤碳酸钙含量较2002年相比降低了48%。苜蓿连作耕层土壤有机质积累显著,与裸地相比增加了134.9%。施肥增加了土壤有效磷含量,粮豆轮作系统中氮磷有机肥配施0-15cm和15-30cm土壤有效磷含量和不施肥相比分别提高了34.3倍和11.69倍。连续施肥条件下土壤胡敏酸与富里酸比值均大于1。施用有机肥增加了土壤还原性物质总量,其中粮豆轮作系统中氮磷有机肥配施耕层土壤增加较多,较不施肥相比增加了107.14%。(2)作物种植和施肥均增加了土壤有效铜、铁含量。施肥可提高土壤有效锰含量。苜蓿、小麦连作以及施用有机肥可显著提高土壤有效锌含量。与2002年相比,2015年耕层土壤有效铜、锰含量增加量最大的分别是小麦连作系统中单施有机肥0.69 mg kg-1、粮豆轮作系统中氮磷有机肥配施58.91%。苜蓿连作耕层土壤有效锌、铁含量较2002年相比分别增加了1.95倍和2.05倍。(3)土壤中微量元素的主要存在形态是矿物态,锰的氧化物结合态所占比例也较大。2015年和2002年相比,铜、锌、铁的形态分布变化不大,而锰的形态分布变化较大,表现为矿物态和交换态锰的占比有所提高,碳酸盐结合态、氧化物结合态、有机结合态锰的占比有所降低。(4)长期种植作物和施肥对土壤锌、铜的活化作用很小,但交换态锰和铁的含量都有所增加。2015年苜蓿连作耕层土壤交换态锰增加最显著,较裸地相比增加了8.03倍。粮豆轮作系统中氮磷有机肥配施耕层土壤交换态铁增加较多,较不施肥相比增加了84.36%。各形态铜、锌含量随作物种植和施肥年限的增加而增加,但矿物态铜仅在施用化肥时有所增加。小麦连作系统中单施有机肥耕层土壤碳酸盐结合态、氧化物结合态、有机结合态铜增加较多,较2002年相比分别增加了2.01mgkg-1、1.7mgkg-1、3.54mgkg-1。苜蓿连作耕层土壤氧化物结合态锌增加较多,较2002年相比增加了94.26%。作物种植仅降低了碳酸盐结合态锰含量。苜蓿连作0-15cm和15-30cm土壤碳酸盐结合态锰含量降低较多,较2002年相比分别降低了59.95mgkg-1和35.65mgkg-1。小麦连作系统中15-30cm土壤有机结合态锰增加显著,较裸地相比增加了2.63倍。小麦连作系统土壤各形态铁都有所增加。不施肥情况下,小麦连作系统中0-15cm和15-30cm土壤碳酸盐结合态铁较2002年相比分别增加了114.52%和183.69%、有机结合态铁分别增加了1.08倍和3.3倍。施肥大都降低了土壤各形态锰和铁的含量。粮豆轮作系统中单施磷肥耕层土壤有机结合态锰增加显著,较不施肥相比增加了8.2倍。(5)长期作物种植和施肥条件下土壤ph值与有效铜、锰、锌、铁之间显著负相关,有效磷、胡敏酸、富里酸与之相反;土壤有机质、还原性物质总量与有效铜显著负相关,与有效锰、锌、铁则相反;土壤水分与有效铜、锌呈正相关,而与有效锰、铁呈负相关。与dtpa-cu、mn、zn、fe含量之间直接通径系数最高的分别为土壤水分0.781、胡敏酸0.652、有机质0.895、有机质0.83。与dtpa-cu、mn、fe含量之间直接负作用较高的分别为还原性物质总量-0.509、富里酸-0.595、碳酸钙-0.501。(6)长期作物种植和施肥条件下交换态铜、锰、铁与有效量间呈正相关,且对有效量的直接通径系数也最高,分别为0.829、0.445和0.122,故交换态是土壤有效量的直接和主要来源。碳酸盐结合态铜与有效铜呈正相关,且与交换态铜间接通径系数最大0.479,表明它可以通过向交换态铜的转化而增加土壤中有效铜的含量。矿物态铜与有效铜直接通径系数较高0.571,可视矿物态铜为土壤有效铜来源的储备库。碳酸盐结合态、有机结合态与有效锰、锌、铁的相关系数、直接通径系数均为正值,表明这两种形态是土壤有效量的来源。氧化物结合态锌与有效锌显著正相关,也是土壤锌的有效来源。(7)长期施用微肥增加了土壤有机质、还原性物质总量。2015年施用铜肥表层土壤有机质和还原性物质总量增加最多,较对照相比分别增加了25%和24.74%。施用微肥后土壤碳酸钙、有效磷、胡敏酸、富里酸含量大都有所降低。施用铜肥0-15cm、15-30cm土壤碳酸钙含量降低最显著,较对照相比分别降低了32.35%、41.25%。施用锌肥表层土壤有效磷含量降低最多,降低了55%。施用微肥后胡敏酸和富里酸比值均小于1。施用锰肥表层土壤胡敏酸含量降低最多,降幅为77.87%。施用锌肥亚表层土壤富里酸含量增幅最大,增加了2.27倍。长期施用微肥后,土壤铜、锌的全量及有效量增加显著,表层积聚现象明显。2015年表层土壤全铜、全锌含量较对照相比分别增加了131.82%和108.71%;有效铜、锌含量较对照相比分别增加了6.03倍和6.97倍。全锰、有效锰含量并没有明显增加。2015年和2001年相比,全锰含量增加幅度小于12%;2015年30-45cm土层有效锰含量和对照相比增幅最大26.54%,其它土层增幅均小于6%。施用微肥后土壤交换态铜、锌占全量的比例增加显著,不同形态锰占全量的比例变化不明显。土壤各形态铜、锰、锌含量随施肥年限增加而增加,尤其是表层土壤,矿物态锰则相反。表层土壤氧化物结合态、碳酸盐结合态铜增幅较大,较对照相比分别增加了23.46倍和16.35倍。各土壤性质与有效铜、锰、锌间相关性不显著,但对微量元素形态有所影响:胡敏酸与除交换态铜之外的其它形态铜以及有机结合态锰都显著负相关;富里酸与氧化物结合态锌显著正相关。有效铜与碳酸盐结合态、氧化物结合态、有机结合态铜显著正相关;交换态铜载荷在第二主成分里最大,这四种形态是土壤有效铜的来源。有效锰与交换态锰显著正相关;第一主成分里氧化物结合态、有机结合态锰的载荷较大,这三种形态与土壤有效锰关系密切。有效锌与交换态、氧化物结合态、有机结合态锌显著正相关,对有效锌贡献较大。(8)施用微肥与土壤微量元素有效量之间存在以下相互作用关系:锌抑制铜,但铜不抑制锌;锰利于铜,而铜抑制锰;锌抑制锰,但锰不抑制锌;锰肥有利于土壤中有效铁含量的增加。
[Abstract]:The study of the effectiveness of trace elements in soil has become the focus of attention in the field of agriculture and environmental science. Fertilization is an important way for trace elements to enter the soil. The relationship between fertilization and the availability of soil microelements can provide scientific reference for agricultural production practice. This paper studies the long-term fertilization conditions. The contents, morphology, distribution characteristics and changes of soil trace elements were analyzed, the factors affecting the availability of soil trace elements were analyzed, and the mechanism of the change of soil trace elements was discussed. The main conclusions were as follows: (1) long term crop and fertilization reduced soil pH value and calcium carbonate content, and increased soil organic content. The soil pH value of Alfalfa continuous cropland soil in.2015 year was most lower than that in bare land, which decreased by 0.44 pH units compared with bare land. Compared with 2002, the content of calcium carbonate in plough soil of grain and bean rotation system was lower than that in 2002. The accumulation of organic matter in the soil of Alfalfa continuous cropland soil was significantly increased by 134.9% compared with that of bare land. In the system, the content of N and P organic fertilizer combined with 0-15cm and 15-30cm increased by 34.3 times and 11.69 times compared with that of no fertilizer. The ratio of soil Hu Min acid to fulvic acid under continuous fertilization was greater than 1., and the total amount of soil reductive substances was increased by organic manure, and the nitrogen and phosphorus organic fertilizer in the crop crop rotation system applied to the soil of the plough layer. Increasing 107.14%. (2) crop planting and fertilization increased soil effective copper and iron content. Fertilization could increase soil effective manganese content. Alfalfa, wheat continuous cropping and application of organic manure could significantly increase the content of available zinc in soil. Compared with 2002, the maximum amount of effective copper and manganese content in the plough soil was increased in 2015. The single application of organic fertilizer 0.69 mg kg-1 in wheat continuous cropping system, nitrogen and phosphorus organic fertilizer in grain and bean rotation system with 58.91%. alfalfa continuous cropland soil available zinc, 1.95 times and 2.05 times more iron than in 2002. (3) the main existence form of trace elements in the soil is mineral state, manganese oxide binding state is also more than the proportion of manganese. Compared to 2002 and 2002, the distribution of copper, zinc and iron changed little, but the distribution of manganese was greatly changed, which showed that the proportion of mineral state and exchangeable manganese increased, and the ratio of the carbonate bound state, oxide bound state and organic manganese was reduced. (4) long-term planting and fertilization on soil zinc and copper activation were very important. In.2015 years, the exchange state manganese and iron content in the exchange state increased most significantly, and increased by 8.03 times compared with the bare land. The nitrogen and phosphorus organic fertilizer in the grain bean rotation system increased the exchangeable iron in the soil of the plough layer more, and increased the 84.36%. form of copper, compared with the non fertilizer application, and the zinc content was planted and applied with the crop. The mineral state copper increased only when the fertilizer was applied, but the combination state of the soil carbonate, the oxide bound state, the organic bound copper increased more in the continuous cropping system of the wheat continuous cropping system, and increased the oxide binding state of the 2.01mgkg-1,1.7mgkg-1,3.54mgkg-1. alfalfa continuous cropland soil, respectively, compared with the 2002. The increase of zinc is more, compared with the increase of the 94.26%. crop in 2002, it only reduces the manganese content in the carbonate bound state. The combined manganese content in the alfalfa continuous cropping 0-15cm and the 15-30cm soils decreases more. Compared with the 2002, the organic bound manganese in the 15-30cm soil in the continuous cropping system of 59.95mgkg-1 and 35.65mgkg-1. is significantly increased. Under the condition of no fertilization, the combination of 0-15cm and 15-30cm soil carbonate in the wheat continuous cropping system increased by 114.52% and 183.69% compared with that of 2002, and the organic bound iron increased by 1.08 and 3.3 times respectively. Manganese and iron content. In the grain and bean rotation system, the organic combined manganese in the soil of single phosphate fertilizer layer increased significantly, 8.2 times higher than that of no fertilizer. (5) the soil pH value was negatively correlated with the effective copper, manganese, zinc and iron under the long-term crop planting and fertilization, and the effective phosphorus, the humic acid and the fulvic acid were the opposite; the soil organic matter and the reductive substance were in the opposite direction. The total amount is negatively correlated with the effective copper, which is opposite to the effective manganese, zinc and iron; the soil moisture is positively correlated with the effective copper and zinc, but is negatively correlated with the effective manganese and iron. The highest direct path coefficient between the dtpa-cu, Mn, Zn and Fe is 0.781, the humic acid 0.652, the organic matter 0.895, the organic matter 0.83. and dtpa-cu, Mn, Fe content. The higher negative effects are the total amount of reductive material -0.509, fulvic acid -0.595, calcium carbonate -0.501. (6) in the long-term crop planting and fertilization conditions, the exchange state copper, manganese and iron are positively correlated with the effective quantity, and the direct path coefficient of the effective quantity is also the highest, respectively 0.829,0.445 and 0.122. The exchange state is the direct and main soil effective quantity. There is a positive correlation between the carbonate bound copper and the effective copper, and the maximum path coefficient of the exchange state copper is 0.479, indicating that it can increase the content of the effective copper in the soil through the transformation of the exchangeable copper. The direct path coefficient of the mineral copper and the effective copper is higher than that of the copper, and the visible copper is the Reserve Bank of the effective copper source of the soil. The correlation coefficient of the combined state of acid, the organic binding state and the effective manganese, zinc and iron, the direct path coefficient are positive, indicating that these two forms are the source of the soil effective quantity. The oxide bound zinc is significantly positively correlated with the effective zinc, and is also an effective source of soil zinc. (7) the long-term application of micro fertilizer increases the soil organic matter and the total amount of reductive substances.2015 The total amount of organic matter and reductive substance in the surface soil of copper fertilizer was increased by 25% and the soil calcium carbonate was increased by 25% and the application of micro fertilizer to the photographic ratio. The content of effective phosphorus, Hu Min acid and fulvic acid were mostly reduced. The content of calcium carbonate in 15-30cm soil was most significantly reduced by 0-15cm, and 32.35 decreased compared with the photographic ratio. %, 41.25%. application of Zinc Fertilizer on the surface soil effective phosphorus content decreased most, decreased the ratio of Hu Min acid and fulvic acid after 55%. application of micro fertilizer was less than 1. application manganese fertilizer surface soil Hu Min acid content decreased most, the decrease of 77.87%. application zinc fertilizer subsurface soil rich acid content increase the maximum, 2.27 times. After long-term application of micro fertilizer, soil copper, The total and effective amount of zinc increased significantly. The surface accumulation was obviously all copper in the surface soil of.2015. The total zinc content increased by 131.82% and 108.71%, respectively. The content of effective copper and zinc increased by 6.03 times and 6.97 times compared with the photographic ratio. Total manganese content and effective manganese content did not significantly increase compared with.2015 years and 2001, the total manganese content increased. The increase was less than 12%. In 2015, the increase of effective manganese content in 30-45cm soil layer was 26.54%, and the increase of other soil layers was less than that of 6%. applying microfertilizer. The proportion of zinc in the total amount increased significantly. Especially in the surface soil, the mineral manganese is the opposite. The surface soil oxide binding state, the carbonate bound copper increased by 23.46 times and 16.35 times compared with the photographic ratio respectively. The correlation between the soil properties and the effective copper, manganese and zinc is not significant, but it has an influence on the form of trace elements: Hu Min acid and other forms except the exchange copper. There is a significant negative correlation between the state copper and the organic bound manganese; fulvic acid has a significant positive correlation with the oxide bound zinc. The effective copper has a significant positive correlation with the carbonate binding state, the oxide bound state and the organic bound copper; the exchange state copper loads are the largest in the second main components, and these four forms are the source of the effective copper in the soil. There is a positive correlation; the three forms are closely related to effective manganese in soil. The effective zinc is positively correlated with the exchange state, the oxide bound state, the organic bound zinc and the effective zinc. (8) the application of micro fertilizer to the effective amount of soil trace elements has the following interaction. Effect: zinc inhibits copper, but copper does not inhibit zinc; manganese is beneficial to copper, but copper inhibits manganese; zinc inhibits manganese, but manganese does not inhibit zinc; manganese fertilizer is beneficial to the increase of effective iron content in soil.
【学位授予单位】：中国科学院研究生院(教育部水土保持与生态环境研究中心)
【学位级别】：博士
【学位授予年份】：2016
【分类号】：S153.6
，
本文编号：2120682
[Abstract]:The study of the effectiveness of trace elements in soil has become the focus of attention in the field of agriculture and environmental science. Fertilization is an important way for trace elements to enter the soil. The relationship between fertilization and the availability of soil microelements can provide scientific reference for agricultural production practice. This paper studies the long-term fertilization conditions. The contents, morphology, distribution characteristics and changes of soil trace elements were analyzed, the factors affecting the availability of soil trace elements were analyzed, and the mechanism of the change of soil trace elements was discussed. The main conclusions were as follows: (1) long term crop and fertilization reduced soil pH value and calcium carbonate content, and increased soil organic content. The soil pH value of Alfalfa continuous cropland soil in.2015 year was most lower than that in bare land, which decreased by 0.44 pH units compared with bare land. Compared with 2002, the content of calcium carbonate in plough soil of grain and bean rotation system was lower than that in 2002. The accumulation of organic matter in the soil of Alfalfa continuous cropland soil was significantly increased by 134.9% compared with that of bare land. In the system, the content of N and P organic fertilizer combined with 0-15cm and 15-30cm increased by 34.3 times and 11.69 times compared with that of no fertilizer. The ratio of soil Hu Min acid to fulvic acid under continuous fertilization was greater than 1., and the total amount of soil reductive substances was increased by organic manure, and the nitrogen and phosphorus organic fertilizer in the crop crop rotation system applied to the soil of the plough layer. Increasing 107.14%. (2) crop planting and fertilization increased soil effective copper and iron content. Fertilization could increase soil effective manganese content. Alfalfa, wheat continuous cropping and application of organic manure could significantly increase the content of available zinc in soil. Compared with 2002, the maximum amount of effective copper and manganese content in the plough soil was increased in 2015. The single application of organic fertilizer 0.69 mg kg-1 in wheat continuous cropping system, nitrogen and phosphorus organic fertilizer in grain and bean rotation system with 58.91%. alfalfa continuous cropland soil available zinc, 1.95 times and 2.05 times more iron than in 2002. (3) the main existence form of trace elements in the soil is mineral state, manganese oxide binding state is also more than the proportion of manganese. Compared to 2002 and 2002, the distribution of copper, zinc and iron changed little, but the distribution of manganese was greatly changed, which showed that the proportion of mineral state and exchangeable manganese increased, and the ratio of the carbonate bound state, oxide bound state and organic manganese was reduced. (4) long-term planting and fertilization on soil zinc and copper activation were very important. In.2015 years, the exchange state manganese and iron content in the exchange state increased most significantly, and increased by 8.03 times compared with the bare land. The nitrogen and phosphorus organic fertilizer in the grain bean rotation system increased the exchangeable iron in the soil of the plough layer more, and increased the 84.36%. form of copper, compared with the non fertilizer application, and the zinc content was planted and applied with the crop. The mineral state copper increased only when the fertilizer was applied, but the combination state of the soil carbonate, the oxide bound state, the organic bound copper increased more in the continuous cropping system of the wheat continuous cropping system, and increased the oxide binding state of the 2.01mgkg-1,1.7mgkg-1,3.54mgkg-1. alfalfa continuous cropland soil, respectively, compared with the 2002. The increase of zinc is more, compared with the increase of the 94.26%. crop in 2002, it only reduces the manganese content in the carbonate bound state. The combined manganese content in the alfalfa continuous cropping 0-15cm and the 15-30cm soils decreases more. Compared with the 2002, the organic bound manganese in the 15-30cm soil in the continuous cropping system of 59.95mgkg-1 and 35.65mgkg-1. is significantly increased. Under the condition of no fertilization, the combination of 0-15cm and 15-30cm soil carbonate in the wheat continuous cropping system increased by 114.52% and 183.69% compared with that of 2002, and the organic bound iron increased by 1.08 and 3.3 times respectively. Manganese and iron content. In the grain and bean rotation system, the organic combined manganese in the soil of single phosphate fertilizer layer increased significantly, 8.2 times higher than that of no fertilizer. (5) the soil pH value was negatively correlated with the effective copper, manganese, zinc and iron under the long-term crop planting and fertilization, and the effective phosphorus, the humic acid and the fulvic acid were the opposite; the soil organic matter and the reductive substance were in the opposite direction. The total amount is negatively correlated with the effective copper, which is opposite to the effective manganese, zinc and iron; the soil moisture is positively correlated with the effective copper and zinc, but is negatively correlated with the effective manganese and iron. The highest direct path coefficient between the dtpa-cu, Mn, Zn and Fe is 0.781, the humic acid 0.652, the organic matter 0.895, the organic matter 0.83. and dtpa-cu, Mn, Fe content. The higher negative effects are the total amount of reductive material -0.509, fulvic acid -0.595, calcium carbonate -0.501. (6) in the long-term crop planting and fertilization conditions, the exchange state copper, manganese and iron are positively correlated with the effective quantity, and the direct path coefficient of the effective quantity is also the highest, respectively 0.829,0.445 and 0.122. The exchange state is the direct and main soil effective quantity. There is a positive correlation between the carbonate bound copper and the effective copper, and the maximum path coefficient of the exchange state copper is 0.479, indicating that it can increase the content of the effective copper in the soil through the transformation of the exchangeable copper. The direct path coefficient of the mineral copper and the effective copper is higher than that of the copper, and the visible copper is the Reserve Bank of the effective copper source of the soil. The correlation coefficient of the combined state of acid, the organic binding state and the effective manganese, zinc and iron, the direct path coefficient are positive, indicating that these two forms are the source of the soil effective quantity. The oxide bound zinc is significantly positively correlated with the effective zinc, and is also an effective source of soil zinc. (7) the long-term application of micro fertilizer increases the soil organic matter and the total amount of reductive substances.2015 The total amount of organic matter and reductive substance in the surface soil of copper fertilizer was increased by 25% and the soil calcium carbonate was increased by 25% and the application of micro fertilizer to the photographic ratio. The content of effective phosphorus, Hu Min acid and fulvic acid were mostly reduced. The content of calcium carbonate in 15-30cm soil was most significantly reduced by 0-15cm, and 32.35 decreased compared with the photographic ratio. %, 41.25%. application of Zinc Fertilizer on the surface soil effective phosphorus content decreased most, decreased the ratio of Hu Min acid and fulvic acid after 55%. application of micro fertilizer was less than 1. application manganese fertilizer surface soil Hu Min acid content decreased most, the decrease of 77.87%. application zinc fertilizer subsurface soil rich acid content increase the maximum, 2.27 times. After long-term application of micro fertilizer, soil copper, The total and effective amount of zinc increased significantly. The surface accumulation was obviously all copper in the surface soil of.2015. The total zinc content increased by 131.82% and 108.71%, respectively. The content of effective copper and zinc increased by 6.03 times and 6.97 times compared with the photographic ratio. Total manganese content and effective manganese content did not significantly increase compared with.2015 years and 2001, the total manganese content increased. The increase was less than 12%. In 2015, the increase of effective manganese content in 30-45cm soil layer was 26.54%, and the increase of other soil layers was less than that of 6%. applying microfertilizer. The proportion of zinc in the total amount increased significantly. Especially in the surface soil, the mineral manganese is the opposite. The surface soil oxide binding state, the carbonate bound copper increased by 23.46 times and 16.35 times compared with the photographic ratio respectively. The correlation between the soil properties and the effective copper, manganese and zinc is not significant, but it has an influence on the form of trace elements: Hu Min acid and other forms except the exchange copper. There is a significant negative correlation between the state copper and the organic bound manganese; fulvic acid has a significant positive correlation with the oxide bound zinc. The effective copper has a significant positive correlation with the carbonate binding state, the oxide bound state and the organic bound copper; the exchange state copper loads are the largest in the second main components, and these four forms are the source of the effective copper in the soil. There is a positive correlation; the three forms are closely related to effective manganese in soil. The effective zinc is positively correlated with the exchange state, the oxide bound state, the organic bound zinc and the effective zinc. (8) the application of micro fertilizer to the effective amount of soil trace elements has the following interaction. Effect: zinc inhibits copper, but copper does not inhibit zinc; manganese is beneficial to copper, but copper inhibits manganese; zinc inhibits manganese, but manganese does not inhibit zinc; manganese fertilizer is beneficial to the increase of effective iron content in soil.
【学位授予单位】：中国科学院研究生院(教育部水土保持与生态环境研究中心)
【学位级别】：博士
【学位授予年份】：2016
【分类号】：S153.6
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本文编号：2120682
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