【作者】 徐钰；

【导师】 张民；

【作者基本信息】 山东农业大学 ， 土壤学， 2008， 博士

【摘要】 波尔多液营养保护剂是山东农业大学主持完成的国家“948”计划“波尔多液营养保护剂制作技术及作物效应研究”项目的研究创新成果,其在传统波尔多液有效成分配比的基础上,配以载体填料和配方助剂,根据需要加入某些微量营养元素,加以浓缩、精制而研制开发的一种具有营养和杀菌双重功能的新型干悬浮剂。该制剂在植株表面附着时间长,不仅能增强其防病抑菌的效果,还可减少一定的喷药量及喷药次数,并且使用、运输及存储方便。另外,由于制剂中添加了少量微量元素,可为作物的生长发育提供营养。波尔多液营养保护剂的上述优势可媲美甚至赶超国内外同类产品,且产品的生产技术成熟,可大批量生产,具有广阔的应用前景。而针对波尔多液营养保护剂使用后所造成的土壤中铜累积及其对土壤环境和作物生长发育的影响是目前亟待研究和解决的问题。本研究采用土柱模拟、解吸试验、室内培养、急性毒理试验、盆栽试验,结合化学连续浸提法和生物统计等手段,系统研究了波尔多液营养保护剂产品有效成分铜在土壤中的垂直迁移、形态转化和解吸特性,深入探讨了产品对作物生长、发育和品质的影响,明确了波尔多液营养保护剂土壤污染表征的生物活性指标,为波尔多液营养保护剂的生产、应用推广和生态安全评价提供理论依据。主要研究结果如下:(1)经pH为7.0和4.0的淋滤液淋溶后,波尔多液营养保护剂有效元素铜仍累积于土柱表层,向下垂直迁移性很小,不会对地下水体产生铜污染。增施有机物料和提高淋溶液酸度会促进土柱中Cu的迁移,尤其是pH为2.0的酸雨模拟淋溶下,土柱中上层Cu被活化主要以交换态发生向下迁移。三种铜制剂中以硫酸铜处理下Cu的迁移速率和程度最大,可迁至10-15cm土层,而波尔多液营养保护剂和美国Kocide2000则主要集中于7-10cm土层;三种铜制剂处理土柱底层15-20cm土壤均未受到铜严重污染。(2)随有机酸浓度升高,草酸和柠檬酸对波尔多液营养保护剂处理的土壤中Cu2+的解吸率增加,尤以柠檬酸对Cu2+解吸的促进作用最强。随着解吸液温度的升高,草酸体系中有利于Cu2+的解吸,而柠檬酸体系中对Cu2+的解吸有抑制作用。随着解吸液pH值的升高,草酸体系中土壤Cu2+的解吸率降低;而柠檬酸体系中土壤Cu2+的解吸率呈降低-升高-再降低的变化。再者,铜制剂处理的潮土(钙质淡色潮湿雏形土)中铜的解吸率显著低于铜制剂处理的棕壤(简育湿润淋溶土),前者中Cu2+的有效性和迁移性显著小于后者。本试验条件下,三种铜制剂处理的土壤中均以波尔多液营养保护剂土壤中Cu2+的解吸量最少,亦对土壤环境带来的影响最小。(3)双常数方程和Elovich方程可用来描述波尔多液营养保护剂处理土壤Cu2+的解吸动力学特性。在有机酸影响下铜制剂处理的棕壤和潮土中Cu2+的解吸速率均较快,60min左右基本达到平衡,且以柠檬酸存在时土壤中Cu2+的解吸速率最大。三种铜制剂处理的土壤相比,以波尔多液营养保护剂处理土壤中Cu2+的解吸初始速率最小。(4)棕壤中施用波尔多液营养保护剂显著增加了土壤中晶质锰氧化物结合态和无定型铁结合态铜,潮土中则主要以铁锰氧化物结合态铜占优。两种土壤上波尔多液营养保护剂处理下交换态铜所占比例要显著小于硫酸铜和美国Kocide2000,铜的有效性最低。随培养时间的延长,棕壤上交换态、有机结合态、晶质锰氧化物结合态和无定型铁结合态铜呈升高趋势,而晶质锰氧化物结合态和残渣态铜则有先升高后降低趋势。潮土上铜形态的转化幅度小,交换态、碳酸盐结合态和残渣态铜总体上呈降低趋势,铁锰氧化物结合态和有机结合态铜呈升高趋势,培养第14天时各形态铜之间的转化基本达到平衡。(5)长期使用铜制剂会对土壤脲酶、蔗糖酶、磷酸酶活性和微生物生物量碳产生不可逆的抑制作用,且生物活性与铜含量呈极显著性负相关,可将其作为波尔多液营养保护剂和其它铜制剂对土壤铜污染程度的生物学指标。以磷酸酶为预警指标,得到棕壤一级土壤预警值为19.26%,二级土壤为22.04%;潮土上分别为7.02%和30.11%。(6)探明了波尔多液营养保护剂处理土壤中铜的各化学形态与土壤生物学指标的关系。棕壤中有机结合态和交换态对土壤酶活性和微生物量碳的影响最大,晶质锰氧化物结合态、无定型铁结合态和晶质铁氧化物结合态也有一定影响。有机结合态、交换态和铁锰氧化物结合态对潮土生化指标都有影响,尤其是前者的贡献最大。因此,综合两种土壤铜形态与生物学性质的关系,在衡量波尔多液营养保护剂对棕壤和潮土铜污染程度时需要考虑铜的交换态和有机结合态。(7)土培试验中,波尔多液营养保护剂对土壤生物学性质的影响与硫酸铜相似,甚至某些酶活性小于硫酸铜,这或许与产品的添加剂对某些土壤生物学性质有一定的抑制作用有关。但在种植作物的土壤上,添加剂的这种抑制作用稍有减弱,产品对土壤生物学性质的影响小于硫酸铜。无论是种植作物的土壤还是没有种植作物的土壤,产品对土壤生物学性质的影响均略大于美国Kocide2000。因此,还应考虑研究添加剂的替代改良品种或用量配比,以便改善产品对土壤生物学性质的影响。(8)波尔多液营养保护剂的长期施用不可避免带来土壤中铜的累积,但铜的有效性小于美国Kocide2000和硫酸铜,由于铜的施用量远小于传统波尔多液,所带来的铜累积污染也会显著减少。产品中微量元素锌的添加,能够显著提高土壤中锌的有效性;而受土壤中高铜浓度的影响,即使产品中添加了铁元素,土壤中铁的有效性仍显著降低。增施有机物料可降低潮土铜的有效性,而提高有效锌和铁的含量。(9)颗粒粉剂型波尔多液营养保护剂与美国Kocide2000因其铜溶解度低对植物发芽的影响小于硫酸铜,三者对作物发芽产生相同抑制率时的铜浓度前两者是后者的2-4倍。因此,在评价粉状铜制剂对环境的影响时,应充分考虑其自身的特点。不同植物对铜制剂污染物的毒性响应具有明显差异,本试验中三种植物对铜制剂的敏感顺序为:油菜>番茄>小麦,可将油菜作为铜制剂污染土壤毒理诊断的指示植物。(10)发芽指标中以发芽指数和根伸长受铜制剂的影响最敏感,与铜浓度呈对数或二次多项式相关,可用于研究铜制剂污染毒性与植物响应的剂量-效应关系。本文潮土中波尔多液营养保护剂对作物种子发芽抑制阈值的铜浓度要明显高于棕壤4-6倍。(11)长期使用铜制剂导致蔬菜可食部分中铜的大量积累,从而影响作物的生长、发育和品质,且在短时间内不会消除。然而,由于波尔多液营养保护剂处理土壤中有效锌含量的增加,提高了菠菜对锌的吸收,从而增加了菠菜体内锌含量。四种铜制剂中,传统波尔多液对作物的影响最大,硫酸铜次之,波尔多液营养保护剂与美国Kocide2000相近。增施3%的有机物料可以缓解波尔多液营养保护剂对植物生长发育的影响,棕壤上三种作物增产26%-192%,潮土上菠菜增产30%-118%。更多还原

【Abstract】 Bordeaux nutritional protective powder (BNPP) is a kind of dry suspending agent, which is based on the effective element rate of Bordeaux mixture, added with additives and assistant materials, then concentrated and refined. Because of the trace element added in the preparation, it could provide nutrition to the crops. Moreover, the preparation could stick to plant surface for a long time, so that it could enhance the effects on preventing and curing germina, reduce the quantity and time of spray, and have other advantages in the manufacturing, applying and storing procedures. Bordeaux nutritional protective powder could be equal even exceed to congeneric product in the word. Furthermore, the maturely productive technique made it be volume-produced, so Bordeaux nutritional protective powder in farming widely use will come true. However, as the effective component of Bordeaux nutritional protective powder—copper applied frequently, the cumulation of copper in soil must be keep track to study the influence of copper on soil property and crop growth.In order to offer academic thereunder for producing, spreading and ecosecurity estimation of Bordeaux nutritional protective powder, several experiments were conducted and sequential extractive method and biostatistical method were used in this study. The vertical transferance, fraction transformation and desorption characterisitcs of copper in soil treated with Bordeaux nutritional protective powder were examined by column simulation, desorption experiment, laboratory incubation. Also, the effects of BNPP on seed germination, growth and development of plants and so on were studied by acute toxicity and pot experiment. The biologic activity index of the soil contamination by Bordeaux nutritional protective powder and other copper agents was definituded. The main results were summarized as follows:(1) Copper, the effective component of BNPP mainly accumulated in top soil after leaching by pH 7.0 and 4.0 leaching water, the upright down transference of copper was small and could not contaminate the groundwater. The moving of copper was accelerated with the increasing of organic materiel and acidity of leaching water, especially leaching by pH 2.0 simulated acid rain. The copper migrating in the soil column was mainly in exchangeable form. The greatest migratory speed and extent was found in CS treatment, which could move to 10-15cm in soil column; copper was mainly accumulated in 7-10cm soil layers in BNPP and KCD treatments. However,soil in the bottom of soil column was not polluted by copper.(2) The desorption rate of Cu2+ from soils treated by three copper-based pesticides increased with increase of concentration of oxalic acid and citric acid, especially of citric acid. The higher temperature was in organic acid desorption solution (except in citric acid), the higher desorption rate of Cu2+ was found in soil. As pH value of desorption solutions increased, Cu2+ desorption rate decreased as oxalic acid was added into soil; in contrast, when citric acid was added into the tested soil, Cu2+ desorption rate decreased at first, then enhanced, and then decreased again, showing as of lying“S”. Furthermore, Cu2+ desorption in the calcareous Fluvo-aquic soil (Och-Aquic Cambosols) was higher than in the Brown soil (Hap-Udic Luvisols), so the effectivity and transference of Cu2+ in the former was less than the latter. Taking all the experiment conditions into account, the Cu2+ desorption rate for three copper-based pesticides soil was CS>KCD>BNPP, and thus soil environment was least effected by BNPP.(3) The best model to describe Cu2+ desorption kinetics in BNPP treated soil was two-constant equations, followed by the Elovich equation. Cu2+ desorption rate from copper-based pesticides treated soil was desorpted so fast that the desorption equilibrium could be reached only after 60 min desorption. Comparing with oxalic acid, desorption rate was greater when citric acid was used. And the least Cu2+ initial desorption rate was found in BNPP treated soil.(4) The application of BNPP significantly increased the ratio of MnOX-Cu and NFe-Cu in the Brown soil (Hap-Udic Luvisols), and the ratio of FeMnOX-Cu in the calcareous Fluvo-aquic soil (Och-Aquic Cambosols). The ratio of EX-Cu in both two kinds of soil treated with BNPP was significantly less than that of CS and KCD. In the incubation, EX-Cu, OR-Cu, MnOX-Cu and NFe-Cu were increased; FeOX-Cu and Res-Cu were increased first then decreased in the Brown soil (Hap-Udic Luvisols). However, the invert extent of copper conformation in the calcareous Fluvo-aquic soil (Och-Aquic Cambosols)was small, EX-Cu, Car-Cu and Res-Cu were decreased, FeMnOX-Cu and OR-Cu were increased, and the transformation of copper reached equilibrium in fourteen days after incubation.(5) The activities of urease, sucrase, acdic phosphatas and the SMBC were irreversibly inhibited by BNPP and the inhibitions were increased with the increasing BNPP dosage. And statistical analysis indicated that there was great remarkable negative relationship between the biological activity and copper content. It was feasible to use them mentioned above as biological index to evaluate BNPP polluted soil. Taking phosphatase as warning index, the threshold value of warning of first-class soil was 19.26%, that of second-class soil was 22.04% in Brown soil; there were 7.02% and 30.11% in Fluvo-aquic soil, respectively.(6) The relationship between copper chemical conformation and biological index in soil treated with BNPP was primarily proved up. In the Brown soil (Hap-Udic Luvisols), the more contributions to inhibiting effect of soil enzymatic activities and SMBC were OR-Cu and EX-Cu; MnOX-Cu, NFe-Cu and FeOX-Cu also had some effects. OR-Cu, EX-Cu and FeMnOX-Cu played an important role in biological index of the calcareous Fluvo-aquic soil (Och-Aquic Cambosols), especially the former. In order to weight the contamination degree of BNPP in both soils, OR-Cu and EX-Cu should be taken into account.(7) In the soil incubation experiment, BNPP made similar effects with CS on soil biological property. Even, some enzyme activity in BNPP were less than CS, these results might attribute to the additives in BNPP. However, the inhibition of additives was reduced in soil with plant growth, and the effects of BNPP on soil biological properties were less than that of CS. But the effects of BNPP on soil biological were still higher than that of KCD not only in soil with plant but also in soil without plant. Therefore, in order to improve the effect of BNPP on soil biological properties, the kinds and dosage proportion of additives should be taken into account.(8) Copper inevitably accumulated in soil for the long term application of BNPP and other copper agents, but the availability of copper in the soil was less than KCD and CS. Furthermore, the availability of zinc in soil was increased; this might contribute to zinc which added in the product. But, soil available iron was significantly decreased for the higher content of copper in the soil even if iron added in the produc. The application of organic matter could reduce the availability of the calcareous Fluvo-aquic soil (Och-Aquic Cambosols) copper, and increase the content of available zinc and iron. (9) The inhibitory effects of BNNP and KCD on the plant seed germination were lower than that of CS, this might be related to their low copper solubility. And the copper concentrations of BNNP and KCD which caused the same inhibitory rate of plant seed germination were 2-4 times than that of CS. So the characteristics of copper-based pesticides should be taken into account as evaluating those effects on the environment. The toxic responses of plants for the copper-based pesticides were significantly different, and the plant sensitive sequence order was cole>tomato>wheat. It was feasible to use cole as indicatory plant to be toxicological diagnosis of soil contaminated with copper-based pesticides.(10) The germination index and root elongation were the most sensitive to copper-based pesticides pollution, and they were significantly related with the copper concentration for logarithmic expression or quadratic polynomial expression. So germination index and root elongation could be applied in the research on the dose-response relationship between pollution toxicity of copper-based pesticides and plant response. In this research, the threshold copper concentration which inhibited the germination of seed in the calcareous Fluvo-aquic soil (Och-Aquic Cambosols) was significant higher 4-6 times than that in the Brown soil (Hap-Udic Luvisols).(11) Copper was accumulated in the edible part of the vegetable, and the growth, development and quality of vegetable were also affected for long term application of copper-based pesticides and these effects could not be eliminated in a short time. The zinc content in the spanich was increased due to the increased content of available zinc in the BNPP treated soil. Plants were affected mostly by BDM, next was CS and the effect of BNPP was a little higher than that of KCD. Organic materials added with the 3% rate in BNPP applied soil could reduce the negative effects of BNPP on plant growth and development. Biomass of crops increased 26%-192% in the Brown soil (Hap-Udic Luvisols), and 30%-118% in the calcareous Fluvo-aquic soil (Och-Aquic Cambosols).更多还原