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喀斯特城市地下水C、N同位素地球化学——污染物迁移和转化研究
李思亮
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
关键词地下水 喀斯特 碳同位素 硝酸盐 氮同位素 氧同位素
摘要中国西南喀斯特地区有突出的地球化学敏感性和生态环境脆弱性等特征,其中水环境污染是喀斯特地区所面临的极其严重的生态与环境问题。水环境生源物质循环过程对于人类生存环境质量的保护和提高有着直接的联系,由于环境体系受多种控制因素影响,利用多同位素方法讨论单一环境体系中物质循环过程和生态环境效应已成为同位素地球化学发展的一个重要趋势。碳、氮同位素已被广泛用于探讨和解决当前的一些重大环境问题,如生源要素生物地球化学对人为污染物的响应、温室气体的来源、湖泊富营养化、地下水硝酸盐污染等。为此本论文利用稳定同位素技术(13C、I5N、18O),以喀斯特城市地下水为主要研究对象,对贵阳雨水中的C、N沉降过程、贵阳/遵义地下水C、N同位素地球化学进行了初步研究。通过以上研究,得到以下的主要认识。1.探讨了贵阳雨水中碳沉降的年变化特征,结果表明贵阳雨水DOC平均值为3.76mg/L,POc平均值为0.54mg/L,含量季节间变化不显著。雨水中DOc与PH呈负相关关系,表明有机碳中酸性成份对酸雨有一定贡献。δ13C-POC取值范围在(-27.0,-24.0‰)之间,季节间差异不大,结合已有研究结果表明雨水中颗粒有机碳主要来源于雨水所冲刷的本地大气颗粒物。2.探讨了贵阳雨水无机氮沉降的年变化特征,结果表明贵阳城区雨水中的NH4+、NO3-、δ15N-NH4+,δ15N-NO3-,δ18O-NO3-,季节性差别都不大。NH4+主要来源于土壤中NH3挥发以及大气颗粒物中按的洗脱,而硝酸盐可能主要来源于燃煤和机动车的排放等,同时气候是影响同位素组成差异性表现的一个重要影响因素。3.初步分析了贵阳与遵义地下水/地表水主要水化学成分,结果证实水体水化学组成主要受研究区水文地质背景控制,即阳离子主要以Ca2+,Mg2+为主,而阴离子以HCO3-,SO42-离子为主。但是有部分水样有较高的人为输入物质K+,Na+,Cl-和NO3-,表明人为活动在研究区内已对地表水/地下水产生一定影响。4.利用碳同位素较好地示踪了地下水溶解无机碳季节变化的主要规律,地下水夏季的DIC含量明显低于冬季DIC含量,这是由于大量降水的稀释作用引起的。地下水DIC夏季一般比冬季更富集12C,表明夏季地下水中生物成因无机碳贡献增加。经计算表明贵阳/遵义地下水来源于碳酸盐风化的无机碳比重大多数大于50%,表明硫酸可能参与风化过程。5.较为系统地探讨了地下水/地表水中有机碳的冬季/夏季演化规律以及受影响因素,地下水大多数样品DOC和POC含量不高,个别受污染样品明显具有较高有机碳含量。大部分夏季地下水δ13C-POC明显大于冬季,表明夏季地下水颗粒有机碳受外源(C4植物碎屑)输入影响。地表水TOC(DOC+POC)与人为输入离子[K+Na++Cl-]呈一定的正相关关系,表明有机碳主要受人为污染影响。6.以贵阳为例,根据δ13CDIC等势图、结合主要水化学特征在空间上的分布可知,贵阳市区中部,东北部及西郊农业区地下水受污染较为严重。表明一定条件下,碳同位素组成可以用来指示区域地下水受人为活动影响范围。7.通过对地下水三氮分析初步掌握了地下水氮污染的基本特征,地下水中NO3-是最主要的无机氮形态,NH4+和NO2-含量大多较低,地下水中具有高NO2-与NH4+的水样比较分散,表明点源污染是主要的。8.利用氮氧同位素示踪了贵阳地下水硝酸盐污染来源的季节变化,同时证实了部分地下水发生反硝化。冬季硝酸盐相对夏季含量较低,并且目SN与夕80的平均值都相对较高,表明夏季受外源氮污染明显,郊区地下水硝酸盐主要受硝态氮肥污染影响,城区地下水硝酸盐污染严重,城市生活排泄物是主要的氮污染源;硝酸盐氮氧同位素联同按氮同位素等可以得知部分地下水中存在明显的反硝化作用。9.利用氮同位素取值分布和季节间频度分布变化初步讨论了遵义地下水硝酸盐污染来源的季节变化。遵义含NO3-较高的地下水主要分布在市区、茅草铺(市东北郊)和新店子一忠庄一带(市东南郊)。夏季地下水硝酸盐δ15N的平均值明显低于冬季,一表明夏季地下水受农业化肥等低δ15N值氮污染源污染。10.两城区地下水受点源污染为主,在局部区域有向含水层面源污染转化的趋势。喀斯特城区地下水中C、N物质的循环对环境变化响应较快,同时受不同区域降雨过程和土壤营养物质过程影响而表现出一定的差异性。
其他摘要In recent years the application of stable isotopes is till growing in environmental studies. Stable isotope composition of carbon and nitrogen have been used extensively to provide information on the solution of a wide variety of environmental problems, such as the affects of contamination to the carbon and nitrogen biogeochemistry, the sources of greenhouse gases, eutrophication, nitrate pollution in groundwater and so on. Using of multi-isotope to trace contaminant transportation and transformation is one of new frontiers in stable isotope geochemistry. The objective of this study was to use stable isotope method (13C, 15N, 18O) and water chemistry approach to (1) evaluate the carbon and nitrogen deposition of rain in Guiyang; (2) understand carbon evolution and the relation with contamination in groundwater system in Guiyang and Zunyi; (3) ascertain the sources of nitrogen pollution in groundwater system in Guiyang and Zunyi. The main conclusions have been summarized as follows: 1. The average concentrations of DOC (dissolved organic carbon) and POC (particulate organic carbon) in rain of Guiyang are 3.76mg C/L and 0.54 mg C/L, respectively. The DOC values have negative correlation with pH, which indicates that organic acid contributes to the acidity of rain in Guiyang. 8I3C-POC of rain ranges from -27.0 to -24.O%o and shows no distinct seasonal variations, suggesting that POC mainly comes from local atmospheric dust. 2. The mean values of NH/ and NO3" of rain in Guiyang are 0.8lmg and 0.51 mg N/L, respectively. The average of 815N-NH4+ is -4.7%o, indicating that volatilization and selective washout of N-bearing material are the major factors. The average of 515N and 818O of nitrate are +1.5%o and +34.2%o, respectively. There are no distinct seasonal variations of isotopes of rain in Guiyang. Nitrate in the precipitation mainly comes from incomplete combustion of fossil fuels and vehicle exhaust. Meanwhile, meteorological conditions play an important role in controlling in isotope fractionation in the precipitation. 3. In ground water Ca2+ and Mg2+are the dominant cations, and HCO3" and SO42' are the dominant anions, suggesting the important contributions principally of carbonate weathering and oxidation of FeS and/or dissolution of gypsum strata to the solutes of ground water. Concentrations of K+, Na+, Cl" and NO3' in some of ground water samples are relatively high, probably due to anthropogenic pollution. 4. Concentrations of DIC (dissolved inorganic carbon) are generally lower in summer than in winter, reflecting the dilution effects of the heavy monsoon rains; The 513C values of DIC in ground water higher in winter than in summer, which suggests that biogenic CO2 makes a larger contribution to the DIC in summer than in winter. The calculated results show that more than 50% of the DIC in ground water is from dissolution of carbonate rocks, which is possible that sulfuric acid plays an important role in weathering of carbonate bedrock. 5. The concentration of DOC and POC in most of groundwater samples are lower than 2.00 mg C/L and 0.50 mg C/L, respectively. The 513C-POC values are higher in summer than in winter, suggesting some particulate organic carbon from C4 plant in summer, There is positive relationship between TOC (DOC+POC) and anthropogenic ions (K++Na++Cl') in surface water, which indicates that the concentration of organic carbon was affected by anthropogenic pollution. 6. 813C of DIC in ground water might be a useful tracer to monitor ground water pollution and the change in ecology of ground water due to anthropogenic pollution. For example, Ground water samples collected from the urban, as well as the northeast and west suburbs of Guiyang city are influenced by contamination according to 813Cdic contour and water chemistry distribution. 7. Nitrate is the major dominant specie of nitrogen in most water samples. But high concentrations of ammonium were detected in sewage effluent and contaminated waters, showing ammonium has become the major species of nitrogen pollution in some water samples, especially in winter. The NCV-N and NH4+-N distribution show the point pollution mainly contributes to the contamination of groundwater. 8. The higher nitrate contents of groundwater samples are mainly located in urban and west suburb of Guiyang. There are average lower concentrations and higher 515N of nitrate in winter than in summer, suggesting there is some nitrogen pollution with lower 815N values input into groundwater system with rain in summer, such as chemical fertilizers. It is concluded that some nitrate fertilizers are the major pollution sources according to lower 815N values and higher 518O values of nitrate in suburbs, and sewage effluents may be the major pollution sources in urban. Denitrification should have happened in the groundwater systems according to 51SN of ammonium, 515N and 818O of nitrate. 9. The higher nitrate contents of groundwater samples mainly are located in urban, northeast and southeast suburbs of Zunyi. There are higher 515N of nitrate in winter than in summer, suggesting there are chemical fertilizers inputting into groundwater system with rain in summer due to developed agriculture. 10. Finally, the point pollution is key problem to groundwater in Guiyang and Zunyi. The carbon and nitrogen evolution in karstic groundwater are mainly affected by precipitation and soil biogeochemical process.
页数117
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/3722
专题研究生_研究生_学位论文
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李思亮. 喀斯特城市地下水C、N同位素地球化学——污染物迁移和转化研究[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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