基于ICP-MS技术对贫铀溶解性能及血样中铂的测定方法的研究
发布时间：2018-08-21 08:02
【摘要】：铀是一种同时具有放射毒性和化学毒性的重金属。天然铀广泛存在于水、食物和空气中。贫铀(Depleted Uranium，DU)是天然铀提取~(235)U后的副产品，它与天然铀在同位素组成上有很大不同，天然铀中~(235)U含量约为0.7%，贫铀中~(235)U的含量是其1/3左右(0.2%~0.3%)。与天然铀一样，DU是放射性重金属，其辐射强度约为天然铀的60%。 贫铀属于长寿命核素，半衰期长达4.5×10~9年(以~(238)U计)，它与天然铀一样，同时具有放射性和重金属毒性，进入体内后，会对肾脏、肺、免疫系统和神经系统有不同程度的损害。贫铀因其密度高、易自燃、价格低廉等优点，在商业和军事领域用途广泛。贫铀武器最初被应用于海湾战争，并自此被广泛应用于现代战争，战后参加过作战任务的士兵相继患上了“海湾战争综合征”，引起了人们对贫铀使用后对人类健康和环境影响的关注。公众摄取铀的途径主要来自食物和饮水，被污染的土壤和水源中的铀可通过食用受污染的动植物或直接吸入等方式进入人体，从而对健康造成危害。因此，当贫铀进入环境中后，其在水体中的溶解性能和在土壤中的迁移规律对评价其健康危害，以及对铀污染修复治理均有重要的指导意义。 本研究通过贫铀氧化物的静态溶解实验和土柱迁移模拟实验，对贫铀氧化物在水环境中的溶解性能和在土壤中的迁移规律分别进行了探究。研究中采用ICP-MS技术，同时测定样品中的铀浓度和~(235)U/~(238)U比值，以此判断贫铀的存在。 ICP-MS因其检出限低、灵敏度高、样品用量少等优点，在金属元素痕量分析方面具有无可替代的优越性。铂类药物是迄今为止应用最广泛的抗肿瘤药之一。在该类药物的研究过程中，建立药代动力学模型，研究用药后药物在体内的分布情况和代谢规律十分必要。铂类药物代谢实验中所采集到的样本量通常很少，在目前测定生物样品中铂的方法中，电感耦合等离子体质谱（ICP-MS）法可以充分满足样品测定需求。本研究应用ICP-MS技术建立了血浆中的铂含量的测定方法，该法可以满足铂类药物在大鼠和比格犬体内药代动力学研究的需要。 本文主要包括三个部分内容： 一、贫铀氧化物溶解性能的初步研究 本研究通过贫铀氧化物的静态溶解实验，对贫铀在正常降雨和模拟酸雨条件下的溶解情况，以及土壤和腐殖酸对贫铀溶解性能的影响进行了考察。分析时采用ICP-MS技术，同时测定样品中的铀浓度和~(235)U/~(238)U比值，以此判断贫铀的溶解情况。 实验分为正常降雨和模拟酸雨(pH=4)两种条件，每种条件下设置三个实验组，分别为贫铀组、贫铀+土壤组和贫铀+腐殖酸组，另外在两种条件下分别设置土壤和腐殖酸的空白组。实验中所用的贫铀氧化物有两种，分别为现场采集的DU氧化物粉末样品和分析纯的八氧化三铀。实验结果显示：对实验组上清液最终pH值进行测定，除了含有腐殖酸的组呈弱酸性以外，其余组呈碱性。在不同时间点对各实验组上清液取样测定其铀浓度和~(235)U/~(238)U值，各实验组的比值结果集中于0.003~0.004范围内，与所添加的贫铀氧化物样品的比值一致。各实验组铀浓度结果显示，单独贫铀粉末在上清液中的溶解度随溶液初始酸度增加而增大；当土壤存在时，初始一段时间内，贫铀在模拟酸雨中的溶解速度低于水中，在足够的时间后，贫铀在酸中的累积溶解量会超出水中；当腐殖酸存在时，贫铀溶解量均很低，至少为单独贫铀组溶解量的几十分之一。实验还发现在正常降雨和模拟酸雨条件下八氧化三铀都比DU氧化物样品具有更好的溶解性能。实验结果说明确实有贫铀氧化物溶解进入了上清液中；酸度增大会提高贫铀的溶解度；在足够的时间条件下土壤的存在能够提高贫铀的溶解性能；腐殖酸对贫铀溶解有强烈抑制作用。现场采集的DU氧化物样品中含有的大量杂质成分包裹或镶嵌在铀氧化物的周围，且其中的铀氧化物粒径大小不一；而八氧化三铀成分单一，粒径均匀，这些形态和成分的差异导致八氧化三铀的溶解性能更好。 二、酸雨条件下腐殖酸对贫铀氧化物在土壤中迁移的影响 铀在土壤中的迁移会受到酸雨和土壤中腐殖酸的影响。在前期研究结果的基础上，本研究进行了模拟酸雨条件下的实验室模拟土柱实验，对酸雨和腐殖酸二者综合作用条件下贫铀氧化物在土壤中的迁移情况进行了研究。 实验中所用贫铀氧化物仍为两种，分别为现场采集的DU氧化物样品和分析纯的八氧化三铀，各设置6个实验组，用pH=4和pH=3的模拟酸雨分别淋洗不添加HA，添加2%HA和添加5%HA的土壤，以土层中土壤的铀浓度和~(235)U/~(238)U同位素比值综合判定贫铀迁移深度。实验结果显示，在pH=4的模拟酸雨淋洗条件下，添加HA的组迁移深度大于不添加HA的组，添加2%HA的组迁移深度最大，这一规律与之前报道的正常降雨条件下一致；而在pH=3的模拟酸雨淋洗条件下，添加HA的组迁移深度却小于不添加HA的组，添加5%HA的组迁移深度最小。在pH值为4的模拟酸雨条件下，HA使贫铀在土壤中的迁移深度增大，有促进贫铀迁移的作用，2%HA组比5%HA组促进效果明显；而在pH值为3的酸雨条件下，HA使贫铀在土壤中的迁移深度减小，有抑制贫铀迁移的作用，5%HA组比2%HA组抑制效果明显。说明酸雨淋洗条件下HA对贫铀迁移的影响不仅与土壤中HA的含量有关，而且与酸度有关。在同样的实验条件下，现场采集的DU氧化物样品和八氧化三铀在土壤中的迁移规律是一致的，但是DU氧化物样品在土壤中的迁移深度要比八氧化三铀小。这是由于DU氧化物样品中有较多的杂质包裹或镶嵌在铀氧化物的周围，使DU氧化物样品在淋洗液中的溶解度降低。所有的实验组中，无论贫铀迁移深度的大小，仍然有90%以上的贫铀集中于表层2cm的土层内。说明对于落在土壤表面的贫铀气溶胶，经过迁移而能达到较大垂直深度的贫铀量是很少的，绝大部分的贫铀仍会停留在土壤的表层。 三、建立ICP-MS测定血浆中铂含量的方法 本研究应用ICP-MS技术建立了血浆中的铂含量的测定方法，该法可以满足铂类药物在大鼠和比格犬体内药代动力学研究的需要。 实验采用直接稀释法处理血浆样品，样品用量少，操作简便。以Ir作为内标元素，Pt元素标准曲线在2~250μg·L~(-1)浓度范围内线性良好，r≥0.9996。测定过程采用自动进样器进样，分析速度快，，分析过程中内标元素Ir的计数稳定（RSD5%），最低检出限低。方法的准确度高，相对误差在±5%范围内，方法的日内精密度和日间精密度高，RSD4.0%。经稀释处理的血浆样品在4℃放置24h、-20℃放置24h冻融和室温放置24h三种条件下的稳定性均好，样品测定准确度高，相对误差在±10%范围内。采用本方法对Wistar大鼠/比格犬血浆样品进行测定，得到了血浆中铂浓度-时间代谢曲线，结果令人满意。本方法同时适用于血浆超滤样品中铂浓度的测定，可以满足铂类药物的临床前药代动力学研究的需要。
[Abstract]:Uranium is a heavy metal with both radiotoxicity and chemical toxicity. Natural uranium is widely found in water, food and air. Depleted uranium (DU) is a by-product of extraction of ~ (235) U from natural uranium. It differs greatly from natural uranium in isotope composition. The content of ~ (235) U in natural uranium is about 0.7%, and that of ~ (235) U in depleted uranium is 1. /3 or so (0.2%~0.3%). Like natural uranium, DU is a radioactive heavy metal whose radiation intensity is about 60%. of natural uranium.
Depleted uranium is a long-lived nuclide with a half-life of 4.5 65 Depleted uranium weapons were originally used in the Gulf War and have since been widely used in modern warfare. Soldiers who participated in post-war operations have developed the Gulf War Syndrome, which has aroused concern about the health and environmental impact of depleted uranium after use. The public's access to uranium comes mainly from food and drinking water. Uranium in contaminated soil and water can enter human body by eating contaminated plants and animals or by direct inhalation, which is harmful to human health. Therefore, when depleted uranium enters the environment, its solubility in water and its migration in soil are important for evaluating its health hazards and remediation of uranium pollution. Guiding significance.
In this study, the solubility of depleted uranium oxides in water and the migration of depleted uranium oxides in soil were studied by static dissolution experiment and soil column migration simulation experiment.
ICP-MS has irreplaceable advantages in trace analysis of metal elements because of its low detection limit, high sensitivity and low sample dosage. Platinum drugs are one of the most widely used antineoplastic drugs so far. In the course of the study of these drugs, pharmacokinetic models were established to study the distribution of the drugs in vivo. The amount of samples collected in the experiment of platinum metabolism is usually very small. Among the current methods for the determination of platinum in biological samples, inductively coupled plasma mass spectrometry (ICP-MS) can fully meet the needs of sample determination. To meet the needs of pharmacokinetics of platinum drugs in rats and beagles.
This article mainly includes three parts:
A preliminary study on the solubility of depleted uranium oxides
In this study, the dissolution of depleted uranium under normal and simulated acid rain conditions and the effect of soil and humic acid on the dissolution of depleted uranium were investigated by static dissolution experiments of depleted uranium oxides. Situation.
The experiment was divided into two conditions: normal rainfall and simulated acid rain (pH=4). Under each condition, three experimental groups were set up, namely depleted uranium group, depleted uranium + soil group and depleted uranium + humic acid group. In addition, a blank group of soil and humic acid was set up under the two conditions. The results showed that the final pH value of the supernatant of the experimental group was determined, except that the group containing humic acid was weak acidic, the other groups were alkaline. In the range of 0.003-0.004, the ratio of depleted uranium oxide to the added depleted uranium oxide is the same. The results of uranium concentration in each experimental group show that the solubility of depleted uranium powder in supernatant increases with the increase of initial acidity of the solution; in the presence of soil, the dissolution rate of depleted uranium in simulated acid rain is lower than that in water for an initial period of time, when it is sufficient. In addition, the cumulative solubility of depleted uranium in acid is higher than that in water. When humic acid exists, the solubility of depleted uranium is very low, at least one-tenth of that in a single depleted uranium group. There are depleted uranium oxides dissolved into the supernatant; the solubility of depleted uranium increases with the increase of acidity; the solubility of depleted uranium can be improved with the presence of soil in sufficient time; humic acid has a strong inhibitory effect on the dissolution of depleted uranium. A large number of impurities in the DU oxide samples collected in the field are encapsulated or embedded in it. Uranium oxide is surrounded by uranium oxide and the particle size of uranium oxide is different, while uranium oxide has a single composition and a uniform particle size. The difference of these morphologies and compositions leads to better solubility of uranium oxide.
Two, the effect of humic acid on the migration of depleted uranium oxides in soil under acid rain.
Uranium migration in soils is affected by acid rain and humic acid in soils. On the basis of previous research results, laboratory simulated soil column experiments under simulated acid rain conditions were carried out to study the migration of depleted uranium oxides in soils under the combined action of acid rain and humic acid.
The depleted uranium oxides used in the experiment are still two kinds, one is DU oxides sampled in situ and the other is analytical pure uranium trioxide. Six experimental groups are set up respectively. The soils with and without HA, 2% HA and 5% HA are leached by simulated acid rain with pH=4 and pH=3, respectively. The uranium concentration and ~ (235) U/~ (238) U isotope ratio in the soils are determined comprehensively. Depleted Uranium Migration depth. The results showed that the migration depth of HA-added group was greater than that of HA-not-added group under simulated acid rain leaching condition of pH=4, and that of 2% HA-added group was the largest, which was consistent with the previous reported normal rainfall condition. However, the migration depth of HA-added group was less than that of acid rain leaching condition of pH=3. Under simulated acid rain with pH 4, HA increased the migration depth of depleted uranium in the soil and promoted the migration of depleted uranium. The migration depth of depleted uranium in the 2% HA group was significantly higher than that in the 5% HA group, but the migration depth of depleted uranium in the soil was decreased and the depleted uranium was inhibited under acid rain with pH 3. The migration of depleted uranium in 5% HA group was significantly inhibited than that in 2% HA group, indicating that the effect of HA on the migration of depleted uranium under acid rain leaching was not only related to the content of HA in soil, but also related to acidity. The solubility of DU oxides in the leaching solution is reduced due to the inclusion of more impurities in the DU oxides or their enclosure around the uranium oxides. In all the experimental groups, more than 90% of the depleted uranium is concentrated on the surface regardless of the depleted uranium migration depth. It is shown that for depleted uranium aerosols falling on the soil surface, the amount of depleted uranium that can reach a greater vertical depth by migration is very small, and most of the depleted uranium will remain on the surface of the soil.
Three, establish a ICP-MS method for the determination of platinum in plasma.
A method for the determination of platinum in plasma was developed by ICP-MS. The method can meet the requirements of pharmacokinetic studies of platinum drugs in rats and beagles.
Using Ir as internal standard element, the standard curve of Pt element has a good linearity in the range of 2~250 ug.L~(-1) concentration, R (>0.9996). The automatic sampler is used in the determination process. The analysis speed is fast, the internal standard element Ir count is stable (RSD 5%) and the lowest detection rate is obtained. The method has high accuracy and relative error within (+) 5%. The intra-day precision and inter-day precision of the method are 4.0%. The diluted plasma samples have good stability under the conditions of 4 (?) C for 24 hours, - 20 (?) C for 24 hours and room temperature for 24 hours. The determination accuracy of the samples is high and the relative error is within (?) 10%. The method was applied to the determination of platinum concentration in plasma samples of Wistar rats/Beagle dogs with satisfactory results. The method is also suitable for the determination of platinum concentration in plasma ultrafiltration samples and can meet the needs of preclinical pharmacokinetic studies of platinum drugs.
【学位授予单位】：中国人民解放军军事医学科学院
【学位级别】：硕士
【学位授予年份】：2013
【分类号】：R144;X132
本文编号：2195072
[Abstract]:Uranium is a heavy metal with both radiotoxicity and chemical toxicity. Natural uranium is widely found in water, food and air. Depleted uranium (DU) is a by-product of extraction of ~ (235) U from natural uranium. It differs greatly from natural uranium in isotope composition. The content of ~ (235) U in natural uranium is about 0.7%, and that of ~ (235) U in depleted uranium is 1. /3 or so (0.2%~0.3%). Like natural uranium, DU is a radioactive heavy metal whose radiation intensity is about 60%. of natural uranium.
Depleted uranium is a long-lived nuclide with a half-life of 4.5 65 Depleted uranium weapons were originally used in the Gulf War and have since been widely used in modern warfare. Soldiers who participated in post-war operations have developed the Gulf War Syndrome, which has aroused concern about the health and environmental impact of depleted uranium after use. The public's access to uranium comes mainly from food and drinking water. Uranium in contaminated soil and water can enter human body by eating contaminated plants and animals or by direct inhalation, which is harmful to human health. Therefore, when depleted uranium enters the environment, its solubility in water and its migration in soil are important for evaluating its health hazards and remediation of uranium pollution. Guiding significance.
In this study, the solubility of depleted uranium oxides in water and the migration of depleted uranium oxides in soil were studied by static dissolution experiment and soil column migration simulation experiment.
ICP-MS has irreplaceable advantages in trace analysis of metal elements because of its low detection limit, high sensitivity and low sample dosage. Platinum drugs are one of the most widely used antineoplastic drugs so far. In the course of the study of these drugs, pharmacokinetic models were established to study the distribution of the drugs in vivo. The amount of samples collected in the experiment of platinum metabolism is usually very small. Among the current methods for the determination of platinum in biological samples, inductively coupled plasma mass spectrometry (ICP-MS) can fully meet the needs of sample determination. To meet the needs of pharmacokinetics of platinum drugs in rats and beagles.
This article mainly includes three parts:
A preliminary study on the solubility of depleted uranium oxides
In this study, the dissolution of depleted uranium under normal and simulated acid rain conditions and the effect of soil and humic acid on the dissolution of depleted uranium were investigated by static dissolution experiments of depleted uranium oxides. Situation.
The experiment was divided into two conditions: normal rainfall and simulated acid rain (pH=4). Under each condition, three experimental groups were set up, namely depleted uranium group, depleted uranium + soil group and depleted uranium + humic acid group. In addition, a blank group of soil and humic acid was set up under the two conditions. The results showed that the final pH value of the supernatant of the experimental group was determined, except that the group containing humic acid was weak acidic, the other groups were alkaline. In the range of 0.003-0.004, the ratio of depleted uranium oxide to the added depleted uranium oxide is the same. The results of uranium concentration in each experimental group show that the solubility of depleted uranium powder in supernatant increases with the increase of initial acidity of the solution; in the presence of soil, the dissolution rate of depleted uranium in simulated acid rain is lower than that in water for an initial period of time, when it is sufficient. In addition, the cumulative solubility of depleted uranium in acid is higher than that in water. When humic acid exists, the solubility of depleted uranium is very low, at least one-tenth of that in a single depleted uranium group. There are depleted uranium oxides dissolved into the supernatant; the solubility of depleted uranium increases with the increase of acidity; the solubility of depleted uranium can be improved with the presence of soil in sufficient time; humic acid has a strong inhibitory effect on the dissolution of depleted uranium. A large number of impurities in the DU oxide samples collected in the field are encapsulated or embedded in it. Uranium oxide is surrounded by uranium oxide and the particle size of uranium oxide is different, while uranium oxide has a single composition and a uniform particle size. The difference of these morphologies and compositions leads to better solubility of uranium oxide.
Two, the effect of humic acid on the migration of depleted uranium oxides in soil under acid rain.
Uranium migration in soils is affected by acid rain and humic acid in soils. On the basis of previous research results, laboratory simulated soil column experiments under simulated acid rain conditions were carried out to study the migration of depleted uranium oxides in soils under the combined action of acid rain and humic acid.
The depleted uranium oxides used in the experiment are still two kinds, one is DU oxides sampled in situ and the other is analytical pure uranium trioxide. Six experimental groups are set up respectively. The soils with and without HA, 2% HA and 5% HA are leached by simulated acid rain with pH=4 and pH=3, respectively. The uranium concentration and ~ (235) U/~ (238) U isotope ratio in the soils are determined comprehensively. Depleted Uranium Migration depth. The results showed that the migration depth of HA-added group was greater than that of HA-not-added group under simulated acid rain leaching condition of pH=4, and that of 2% HA-added group was the largest, which was consistent with the previous reported normal rainfall condition. However, the migration depth of HA-added group was less than that of acid rain leaching condition of pH=3. Under simulated acid rain with pH 4, HA increased the migration depth of depleted uranium in the soil and promoted the migration of depleted uranium. The migration depth of depleted uranium in the 2% HA group was significantly higher than that in the 5% HA group, but the migration depth of depleted uranium in the soil was decreased and the depleted uranium was inhibited under acid rain with pH 3. The migration of depleted uranium in 5% HA group was significantly inhibited than that in 2% HA group, indicating that the effect of HA on the migration of depleted uranium under acid rain leaching was not only related to the content of HA in soil, but also related to acidity. The solubility of DU oxides in the leaching solution is reduced due to the inclusion of more impurities in the DU oxides or their enclosure around the uranium oxides. In all the experimental groups, more than 90% of the depleted uranium is concentrated on the surface regardless of the depleted uranium migration depth. It is shown that for depleted uranium aerosols falling on the soil surface, the amount of depleted uranium that can reach a greater vertical depth by migration is very small, and most of the depleted uranium will remain on the surface of the soil.
Three, establish a ICP-MS method for the determination of platinum in plasma.
A method for the determination of platinum in plasma was developed by ICP-MS. The method can meet the requirements of pharmacokinetic studies of platinum drugs in rats and beagles.
Using Ir as internal standard element, the standard curve of Pt element has a good linearity in the range of 2~250 ug.L~(-1) concentration, R (>0.9996). The automatic sampler is used in the determination process. The analysis speed is fast, the internal standard element Ir count is stable (RSD 5%) and the lowest detection rate is obtained. The method has high accuracy and relative error within (+) 5%. The intra-day precision and inter-day precision of the method are 4.0%. The diluted plasma samples have good stability under the conditions of 4 (?) C for 24 hours, - 20 (?) C for 24 hours and room temperature for 24 hours. The determination accuracy of the samples is high and the relative error is within (?) 10%. The method was applied to the determination of platinum concentration in plasma samples of Wistar rats/Beagle dogs with satisfactory results. The method is also suitable for the determination of platinum concentration in plasma ultrafiltration samples and can meet the needs of preclinical pharmacokinetic studies of platinum drugs.
【学位授予单位】：中国人民解放军军事医学科学院
【学位级别】：硕士
【学位授予年份】：2013
【分类号】：R144;X132
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