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土壤中重金属活动性的唐南膜测定、模型模拟与污染的原位控制
其他题名Determining and modeling the free concentrations of heavy metals ions in soil and controlling the pollution in situ
易丽
学位类型博士
2005
学位授予单位中国科学院地球化学研究所
学位授予地点中国科学院地球化学研究所
学位名称博士
学位专业地球化学
关键词土壤 重金属活动性 游离重金属离子浓度 赤泥
摘要土壤是自然环境的重要组成部分,是人类赖以生存与发展的宝贵资源。但是近年来我国土壤重金属污染日益严重,重金属污染物与其它类型的污染物相比具有隐蔽性、长期性与不可逆性等一系列特殊性,成为土壤中永久的污染物,最终通过食物链的传递进入人体,对人类的健康造成潜在的危害。因此,研究土壤重金属污染与控制具有很重要的意义。本论文首次将唐南膜平衡法(DonnanMembraneTechnique)和EcosAT(EquilibriumCalculationOfSpeciationAndTransport)模型引入我国土壤重金属活动性研究,并将两种方法获得的结果进行比较,互相验证,取得了较好的结果。还将两种方法结合探讨了贵州铝厂生产的赤泥对土壤中的游离重金属离子浓度的影响。土壤样品采于贵州都匀福锌矿地区,一个位于锅锌矿选厂尾矿坝下农田中的水稻土,以下简称坝下土,为重污染土;另一个位于锅锌矿上游桥边农田中的水稻土,以下简称桥边土,为轻污染土,本研究取得的主要结论与认识包括:1.作者对唐南膜平衡法进行了部分改进,用国内生产的JAM一I型均相离子交换膜替换Brwin等所用的BDH膜,既降低了实验的平衡时间,又经济实惠。另外还用KNO3溶液代替KNO3和Ca(NO3)2混合溶液作为实验的介质溶液,就可以避免由于国内土壤中Ca2+含量差异较大可能造成的误差。其它实验条件为:蠕动泵的流速为2.0ml/min,平衡时间为48小时。2.用柠檬酸体系(液一液体系)和土壤一水体系(固一液体系)检验了唐南膜平衡法,它可以在不扰动体系平衡的基础上同时测定同一体系中的多个游离金属离子浓度,而且各金属离子之间互不干扰。3.桥边土中的游离重金属离子浓度与其中2mol/LHNO3提取的重金属总含量成很好的直线关系,其中Cu和Zn游离离子浓度与其中的总金属含量呈现较好的正比关系,随着重金属总含量的降低,即土液比的降低,游离重金属离子浓度随之降低;而其中的Ni和Cd却相反,随着重金属总含量的降低,游离重金属离子浓度反而增加。添加赤泥后随着土液比的降低各重金属的游离离羲?子浓度的变化趋势与添加赤泥前一样。桥边土中的重金属游离离子浓度在添加联合法赤泥后有所增加,而拜尔法赤泥的加入降低了其中的游离重金属离子浓度,加入的比例越大,变化的量越多,而且其中Ni和cd的变化幅度比Cu和Zn的要大。4.坝下土中Cu、Zn、Ni和Cd元素的游离离子浓度与它们在土壤中Zmol/LHNo3提取的重金属总含量呈很夯的正比关系,随着重金属总含量的降低,游离重金属离子浓度随之降低。添加赤泥后其中Cu和Zn元素的变化趋势与添加赤泥前一样,Ni和Cd元素出现了异常,Ni在赤泥添加比例为0.50%时变化趋势一样,但添加比例为2.00%时其离子浓度先增加,但在土液比为1:100时反而有较大幅度的降低。而其中Cd离子浓度先增加,在土液比为1:100时反而有较大幅度的降低。坝下土中Cu和Zn的游离离子浓度在添加赤泥以后改变很小,赤泥添加比例为2.00%的土壤中的游离离子浓度相对较低一点,而添加比例为0.50%的与未加赤泥的土壤基本上一样;其中Ni和Cd的变化相对来说较大,赤泥添加比例为2.00%的土壤中的游离离子浓度降低得比较明显,拜尔法赤泥添加比例为0.50%的土壤也得到了较大的改善,而联合法赤泥添加比例为0.50%的却比未加赤泥的土壤中的还要高一点。5.利用ECOSAT模型模拟了本论文所涉及的实验中的游离重金属离子浓度,测量值与模拟值取得了较好的一致,除了Zn的误差较大以外,其它三个元素符合的很好,从而表明EC0sAT在土壤一水系统中的模拟取得了较好的结果。6.模拟了不同土液比土壤中各重金属元素在有机质、铁氧化物、粘土和唐南凝胶体这四种吸附相中的分配。发现在所研究的土壤样品中所有元素在粘土相中所占的比例很小,可以忽略不计,Cu主要分布在有机质相中,占80%左右,随着土液比的降低,其在有机质和唐南凝胶体相中的分配比例慢慢变小,而在铁氧化物中的比例越来越大;Zn主要分布在有机质和铁氧化物相中,各占40%左右;随着土液比的降低,Zn在有机质相中的比例增大,铁氧化物比例几乎不变,而唐南凝胶体所占比例逐渐减小;Ni基本上只分布在有机质和铁”氧化物相中,Cd则几乎只存在于有机质相中,它们的分布比例几乎不随土液比的改变而变化。7.无论在桥边土和坝下土中添加何种赤泥,添加的比例是多少,在添加赤泥前后土壤中重金属元素在各吸附相中的分配比变化很小,主要是有机质相所占比例稍微变小,而铁氧化物相相应的有一点增加。而对于不同的土液比,其变化趋势相同,只是变化幅度相对来说较大。
其他摘要Soil is one of the major components of the environment, by which human's survival and development could maintain. But pollution of heavy metals in soil has been more and more serious during recent several decades. Comparing with the other pollutants, heavy metal pollutants are of special characters, such as covered, long-term and irreversible, for which they became permanent pollution in soil, and they would ultimately harm to health of mankind through food chain, so study and control of the heavy metals pollution are of great significance. In this research, Donnan Membrane Technique and a computer program named ECOSAT (Equilibrium Calculation Of Speciation And Transport) were used to study the mobility of heavy metal ions in soil for the first time in China. The results of both methods were compared and validated with each other. In addition, red muds, which were produced by the Aluminous production Plant of Guizhou, were used to control the mobility of heavy metals in soil. Two soils were studied at different soil solution ratio, one is the soil around a bridge (QBT for short), the other lies underside the smelting factory (BXT for short hereinafter) in Duyun, Guizhou province. BXT is polluted badly, but QBT pollution is light. From these studies, we have obtained the several conclusions as following: 1. Some experimental conditions for Donnan Membrane Technique were improved. JAM-I homogeneous ion exchange membrane, which is made at home, replaced BDH membrane that was used by Erwin. By using the JAM-I homogeneous ion exchange membrane, the equilibrium time become shorter, furthermore it is cheap and can be obtained easily. The mixed solution of KNO3 and Ca(NO3)2 was displaced by KNO3 solution used as the background electrolyte. Error brought by the difference of Ca concentration was avoided. The other conditions for Donnan Membrane Technique were as following. The flow velocity of the peristaltic pump is 2.0mI/min.The equilibrium time is 48 hours. 2. Donnan Membrane Technique succeeded not only in citric acid systems, but also in soil-water system. Several metals could be measured simultaneously with this method, without disturbing the balance between the measured system and the round condition, moreover, all the metals did not interfere each other. 3. The concentrations of free heavy metal ions in QBT were in line with the total metals that were distilled through 2mol/L HNO3. The concentrations of free copper and zinc ions were in direct ratio with the total metals, and they decreased with the decreasing of the total metals, i.e. soil solution ratio. The changes of the concentrations of free nickel 'and cadmium ions were contrary to those of the copper and zinc ions. With the decreasing of the soil solution ratio, the trend of change was the same after adding red muds into it. The concentrations of free heavy metal ions increased after appending red mud derived from confederate process, but decreased after appending red mud derived from Bayer process. The larger the ratio adding was, the more the concentration changed, and the concentration changes of nickel and cadmium ions were larger than those of the copper and zinc ions. 4. The concentrations of free heavy inetals ions were in direct ratio with the total metals, which were distilled through 2mol/L HNO3 in BXT, and they decreased with the total metals. After appending red muds into it, the free concentrations of copper and zinc ions changed little, but those of nickel and cadmium ions changed out of the way. For the concentrations of free nickel ion, it changed as before after adding red muds at the ratio of 0.50%, while it increased firstly after appending red muds at the ratio of 2.00%, but decreased largely at the soil solution ratio of 1:100. For cadmium ion, it changed as nickel ion at the ratio of 2.00%. The concentrations of free copper and zinc ions in BXT decreased little after appending red muds at the ratio of 2.00%, and hardly changed at the ratio of 0.50%. While the cpncentrations of free nickel and cadmium decreased obviously after appending red muds at the ratio of 2.00%. The change of the concentration was still biggish after appending red muds derived from Bayer process at the ratio of 0.50%, but smaller than that of 2.00%. While the concentrations of free cadmium ions increased after appending red mud derived from confederate process at the ratio of 0.5 0%. 5. All experiments processes were modeled through ECOSAT. The results of modeling and measuring were consistent, except .for Zn ion. Thereby we conclude that ECOSAT is a good model to study the soil-water system. 6. Contributions of soil sorbents to the heavy metals adsorptions were modeled through ECOSAT at different soil solution ratio. The sorbents in soil included soil organic matter, iron hydroxides, clay and the Donnan gel of soil organic matter. It -. showed that the contribution bound to clay was very little, and could be neglected. Copper was mainly contributed in soil organic matter, and accounting 80%. With the decreasing of the soil solution ratio, the contributions of copper bounded to soil organic matter and the Donnan gel of soil organic matter decreased slowly, but the contribution bounded to iron hydroxides increased. Zinc was mainly contributed in soil organic matter and iron hydroxides, and accounting 40% respectively. With the decreasing of the soil solution ratio, the contribution of zinc bounded to soil organic matter increased little, and the contribution bounded to iron hydroxides was not changed, but the Donnan gel of soil organic matter decreased slowly. Nickel was mainly bounded to the soil organic matter and iron hydroxides, and cadmium was almost bounded to the soil organic matter. The contributions of nickel and cadmium were not affected by the soil solution ratio. 7. No matter what kind of red muds and how much was the ratio appending in soil, all heavy metals contributing in'the soil sorbents changed a little after adding red muds into soil. The proportion of soil organic matter decreased little, while the proportion of iron hydroxide increased correspondingly. In different soil solution ratio, the trend of change was same, but the range was larger
页数110
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/3718
专题研究生_研究生_学位论文
推荐引用方式
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易丽. 土壤中重金属活动性的唐南膜测定、模型模拟与污染的原位控制[D]. 中国科学院地球化学研究所. 中国科学院地球化学研究所,2005.
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