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粪肥腐解过程不同溶性腐殖物质结合态铜锌的动态变化

Dynamics of Humus Complexed Copper and Zinc during Manure Composting

【作者】 卢丽兰

【导师】 王旭东;

【作者基本信息】 西北农林科技大学 , 土壤学, 2009, 硕士

【摘要】 以鸡粪为材料,添加不同比例的铜锌进行腐解试验,研究了腐解过程中不同溶性腐殖质及其结合态铜、锌(水溶性、氢氧化钠溶性、氢氧化钠-焦磷酸钠溶性)浓度的动态变化,铜、锌之间的形态竞争,腐殖质结合态铜、锌与有效性的关系,铜、锌浓度对腐殖质转化的影响。旨在揭示粪肥腐解过程的腐植物质和重金属的转化规律,为粪肥的安全处理和施用奠定基础。(1)研究了粪肥腐解过程不同溶性腐殖质结合态铜的变化及其受腐解时间和加入铜、锌浓度的影响。粪肥原样中水溶性腐殖质结合态铜(H2O-Cu)占其全铜量的10.97%,在腐解过程中先上升后下降;随着粪肥中添加铜量的增加(1: 1、2: 1、3: 1处理),H2O-Cu占其全铜的比例相应减少了;H2O-Cu浓度随着腐解时间延长呈增加趋势,随粪肥中添加铜量的增加而增加。锌对H2O-Cu含量的影响与腐解进程有关,在腐解的前期H2O-Cu浓度随粪肥中锌含量的增加而增加,在腐解的后期(45、60d),H2O-Cu浓度随粪肥中锌含量的增加而降低。粪肥原样中NaOH浸提的腐殖质-铜(NaOH-Cu)占其全铜量的70.87%,随腐解进行其比例大幅度下降。添加铜锌处理,NaOH-Cu占其全铜的比例随着加入铜的增大而有所下降,且随着腐解时间延长呈下降趋势;NaOH-Cu浓度随腐解时间逐渐下降,随粪肥中铜浓度增加而上升。粪肥中NaOH-Cu浓度受锌含量变化影响较小。粪肥原样中NaOH-Na4P2O7提取腐殖质结合态铜(NaOH-Na4P2O7-Cu)占其全铜量的24.29%,随腐解过程呈增加趋势,添加铜锌的处理的NaOH-Na4P2O7-Cu占其全铜的比例随着加入铜的增大而有所增加,且随着腐解时间延长呈上升趋势;NaOH-Na4P2O7-Cu浓度随着加入铜量的增加而增加,且随腐解进程逐渐增加,NaOH-Na4P2O7-Cu随粪肥中锌含量增加而增加。相关性分析结果表明:H2O-Cu、NaOH-Cu和NaOH-Na4P2O7-Cu之间为显著正相关,它们与有效铜之间呈显著正相关关系。(2)探讨了粪肥腐解过程的不同溶性腐殖质结合态锌的变化及其受腐解进程和加入锌、铜的影响。粪肥原样中水溶性锌(H2O-Zn)占其全锌量的0.74%,在腐解过程中逐渐下降。随着粪肥中添加锌量的增加(Cu/Zn为1: 1、1: 2、1: 3处理),H2O-Zn绝对含量也相应增加,同时随着腐解时间延长呈减少趋势。H2O-Zn含量随铜含量的增加而增加。粪肥原样中NaOH浸提的锌含量占其全锌量的62.41%,在腐解过程其比例大幅度下降;NaOH溶性腐殖物质结合态锌(NaOH-Zn)随着加入锌的增大而有所增加,随着铜含量增加也有增加趋势,而随着腐解时间呈下降趋势。粪肥原样中NaOH-Na4P2O7提取腐殖物质络合锌(NaOH-Na4P2O7-Zn)含量占其全锌量的13.59%,随腐解时间推移呈增加趋势;NaOH-Na4P2O7-Zn的量随着加入锌量的增加,其变化不大。铜含量对NaOH-Na4P2O7-Zn的的量影响很小。随着锌含量增加,H2O-Zn和NaOH-Zn的分配比例逐渐增加,而NaOH-Na4P2O7-Zn的分配比例减少。H2O-Zn、NaOH-Zn与有效锌浓度之间呈极显著或显著正相关,而NaOH-Na4P2O7-Zn与H2O-Zn、NaOH-Zn和有效锌呈极显著或显著负相关。(3)探明了粪肥腐解过程腐殖物质变化。随着腐解的进行,鸡粪中可提取性的有机碳(H2O-C、NaOH-C、NaOH-Na4P2O7-C)总体呈下降趋势,与TOC(总有机碳)含量变化趋势一致。H2O液浸提的腐殖质碳(H2O-C)占可提取腐殖质碳的8%~20%左右,H2O-C分配比随腐解时间延长而减少。随着粪肥中锌含量其变化较小,随着铜含量增加而减小。在腐解整个过程中,NaOH液浸提的腐殖质碳(NaOH-C)占可提取腐殖质碳的50%~70%左右,随腐解时间延长而增加。随着粪肥中锌含量的增加,NaOH溶性腐殖质碳在整个腐解期平均分配比例有所增加,随着粪肥中铜浓度的增加,NaOH溶性腐殖质碳分配比有所下降。NaOH-Na4P2O7液浸提的腐殖质碳(NaOH-Na4P2O7-C)占可提取腐殖质碳的20%~30%左右,NaOH-Na4P2O7-C分配比随腐解时间延长而下降。随着粪肥中锌含量的增加而下降,随着铜含量增加其变化不大。总之,NaOH溶性腐殖质碳在整个腐解期平均分配含量有所增加,而H2O溶性腐殖质碳有所减少,但NaOH-Na4P2O7溶性腐殖质碳的变化较小。粪肥中Cu、Zn的浓度影响到浸提掖中胡富比(HA/FA)变化。水溶性的HA/FA随着铜含量(1:1,2:1,3:1)增加而下降,随着锌含量(1:1,1: 2, 1: 3)增加而增加;NaOH-HA/FA随着铜含量增加而增加,随着锌含量的增加,其变化不明显;NaOH-Na4P2O7-HA/FA随着铜含量增加而增加,也随着锌含量的增加而增加。

【Abstract】 Chicken manure added with Cu and Zn was used for a composting experiment to study the dynamics of soluble humus copper complexes and zinc complexes (expressed as H2O-Cu, NaOH-Cu, NaOH-Na4P2O7-Cu). The competitive relationship of zinc and copper and the relationship between humus-complexed copper and available Cu were also investigated. Study on The changes of humic substance and the effect of high copper and zinc concentrations on the transformation of humic substance. The results showed the change pattern of transformation between humic substance and heavy metal in the composting process. This provides a theoretical base for safe treatment and use of manures.(1) The changes of different soluble humic copper complexes and the effect of composting time and Cu and Zn contents on humic copper complexes were revealed. The study showed that water-soluble humic complexed copper (H2O-Cu) in raw manure accounted for 10.97% of total copper in the compost, increasing during the first 45 days of composting and decreasing thereafter. As the added copper content increased in the treatments such as 1: 1, 2: 1 and 3: 1, the relative H2O-Cu content decreased ,and increased with composting . H2O-Cu concentration increased with the added copper content increasing, and H2O-Cu concentration increased as the added Zinc content increased at first stages of compost, but adding zinc to the manure resulted in a decrease of H2O-Cu concentration at the later stages of composting (45, 60 days). NaOH-Cu accounted for 70.87% of total copper in raw manure and decreased greatly as the composting proceeded. With the added copper content increasing in the manure, the percentage of NaOH-Cu to total copper decreased. During decomposition, NaOH-Cu also decreased. NaOH-Zn concentration gradually decreased with composting time, and increased with the Copper content increasing, but the added zinc levels had no significant effect on NaOH-Cu. NaOH-Na4P2O7-Cu accounted for 24.29% of total copper in the raw manure, increasing with composting time. With the added copper content increasing in the manure, the percentage of NaOH-Na4P2O7-Cu to total copper increased, and showed an increasing trend with composting time. NaOH-Na4P2O7-Cu concentration increased with copper content and composting time increasing , and as adding zinc increased NaOH-Na4P2O7-Cu also increased. Correlation analysis showed:H2O-Cu,NaOH-Cu and NaOH-Na4P2O7-Cu were significantly correlated to each other, and all were significantly correlated to DTPA-Cu (P≤0.01).(2) The changes of different soluble humic copper complexes and the effect of composting time and Cu and Zn contents on humic copper complexes were discussed.. The results showed that water-soluble humic complexed zinc (H2O-Zn) of raw manure accounted for 0.74% of total Zinc of the compost, decreasing with the manure composting. With the increase of zinc content in the treatment such as1: 1, 1: 2 and 1: 3, H2O-Zn increased, showing a decrease trend with decomposition process. The average percentages of H2O-Zinc to total Zinc of the treatment of 1: 1, 1: 2 and 1: 3 were lower than that of the control (raw materials). H2O-Zn was increased with the increase of copper content. NaOH-Zn accounted for 62.41% of total Zinc of the raw manure and decreased greatly with the compost proceeding. With the added Zinc content increasing in manure, NaOH-Zn increased, but decreased with decomposing process. During decomposition, the added copper increased the content of NaOH-Zn. NaOH-Na4P2O7-Zn accounted for 13.59% of total copper of the raw manure, which increased with time of composting. With the added Zinc content increasing in compost manure, the percentage of NaOH-Na4P2O7-Zn to total Zinc changed slightly. The added copper had no significant effect on NaOH-Na4P2O7-Zn. With the added zinc contents increasing in compost manure, the distribution percent of NaOH-Na4P2O7-Zn (Pressed as percent of extracted Zn) decreased and that of H2O-Zn and NaOH-Zn increased. Correlation analysis showed:H2O-Zn,NaOH-Zn, and DTPA-Zn were positively correlated to each other and all were negatively correlated to NaOH-Na4P2O7-Zn. (P≤0.01).(3) The changes of humic substance during manure composting were investigated. With manure decomposition, the extractable organic carbon showed decrease trend in chicken manures, which was similar to trend of Total organic carbon. The H2O humic Carbon (H2O-C) accounted for 8%~20% of extracted humic carbon,and dereased with the copper content and composting time, but had no great change with the zinc content increasing.The greatest amounts of humus-C was present in NaOH faction, accounting for 50%~70%, increasing with composting time. With the zinc content increasing, the average content of NaOH humic Carbon(NaOH–C)increased in the whole composting process, but NaOH–C distribution ratio decreased with copper content increasing. The NaOH-Na4P2O7 humic Carbon (NaOH-Na4P2O7-C) accounted for 20%~30% of extracted humic carbon,and decreased with the zinc content and composting time, but had no great change with the copper content increasing,but that of NaOH-Na4P2O7-C decreased, and that of H2O-C had a little change. In a whole,the average content of NaOH-C also increased in the whole composting process, and that of H2O-C decreased, NaOH-Na4P2O7-C varied small. High Cu and Zn concentrations to the extent may affect the level of HA/FA. The value of water HA/FA ratio decreased with copper content increasing, but increased with zinc content increasing. The value of NaOH HA/FA ratio increased with copper content increasing, but changed little with zinc content increasing. The value of NaOH-Na4P2O7 HA/FA ratio increased with copper and zinc content increasing.

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