陕西“二华”地区浅层地下水水化学特征及其微污染水处理研究
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摘要
陕西省华县、华阴(简称“二华”)地区，地处秦岭山前与渭河下游之间的夹槽低洼地带，其地下水既受秦岭山前水的影响又受渭河河水侧向补给的影响，地下水水化学成分复杂，水质较差，“二华”地区居民生活、生产用水主要使用10m～30m的浅层地下水，水源未经任何处理。本文以“渭河傍河水源地水质演化特征研究”课题为依托，综合应用水文地球化学、水文地质学、同位素水化学、物理化学的理论与方法，全面、系统地研究了“二华”地区浅层地下水水化学特征、水循环规律、演化机制、渭河河水对其水质的影响并对研究区水质进行了评价。此外，针对“二华”地区浅层地下水主要微污染物超标组分，提出采用臭氧―砂碳―锰砂工艺流程，完成了对各流程去除微污染物的室内试验研究，得到了该流程去除微污染超标物的最佳工艺。
研究“二华”地区浅层地下水水循环规律，揭示其水化学特征，寻求适合该地区微污染浅层地下水处理工艺，对当地地下水水资源评价、合理开发利用以及居民生活、生产用水安全都具有重要的理论和生产实际意义。本文主要研究结论如下：
(1)研究区浅层地下水水化学类型、矿化度及硬度分布特征为：
由南向北，即从秦岭北麓到渭河沿岸，水化学类型由简单到复杂，主要从HCO_3·SO_4-Ca·Mg经SO_4·HCO_~(3-)Na·Ca过渡到SO_4·Cl-Na型；由西向东，即沿渭河流向，水化学类型变化不大，靠近秦岭山前，水化学类型以HCO_3·SO_4-Ca·Mg和HCO_3·SO_4-Ca·Mg·Na型为主，靠近渭河，水化学类型以SO_4·Cl-Na和SO_4·HCO_~(3-)Na·Ca型为主。
研究区渭河沿岸下庙街、王宿、华阴农场一带总溶解固体(TDS)较大，水质矿化度较高，为微咸水分布区；靠近秦岭山前、研究区中部TDS较小，为淡水分布区。
研究区地下水硬度普遍偏大，其中以下庙街、华阴农场、七连、夫水一带为极硬水分布区，整体上从南向北，水质从硬水过渡到极硬水。
(2)离子摩尔浓度比值γCl-/γCa~(2+)、γNa~+/γMg~(2+)、γCl-/γSO_4~(2-)和γCl-/γHCO_~(3-)表明：研究区靠近秦岭山前由西向东水动力条件逐渐较弱，渭河沿岸，水动力条件逐渐较强；TDS与Na~+变化一致，即TDS高的地方，Na~+离子的含量占优势；研究区由南向北方向上呈易溶盐的累积过程，水质总体向咸化方向发展。(3)针对研究区水文地质参数较少的原因，应用同位素δ18O、δD值分析研究区浅
层地下水水循环规律，研究表明：研究区在靠近秦岭山前的浅层地下水主要补给源为大气降水；研究区横向由西向东、纵向由南向北路径上浅层地下水的δ18O、δD分布规律反应了其径流规律：即径流由南向北，渭河沿岸地区王宿、下庙街、华阴农场一带存在地下水漏斗区，渭河河水侧向补给该区域；段村街一带，由于该区域地表水丰富，浅层地下水接受地表水的补给。
(4)采用可变模糊集理论评价了研究区水质，根据《地下水质量标准》(GB/T14848-1993)，IV类水质水占总评价水质的64.0%。研究区由南向北，浅层地下水水质类别由II类过渡到IV类，水质逐渐变差；由西向东，水质类别变化不大，基本为IV类；渭河水质与其沿岸浅层地下水水质属相同类别，但是，渭河河水水质要劣于沿岸浅层地下水水质。
(5)针对研究区水质属微污染水，水质主要超标指标为浊度、色度、金属离子锰，提出将臭氧―砂碳―锰砂组合工艺作为对微污染试验用水的处理流程，结果表明：臭氧阶段的氧化作用，对微污染水中的色度、锰离子的去除率为80.0%和17.7%；砂碳层将浊度、色度进一步降低，达到了I类饮用水水源标准；经过高锰酸钾改性的锰砂层，对锰离子去除后，水质达到II类～III类饮用水水源标准，其对锰离子吸附动力学模型符合一级吸附式和Elovich方程，吸附热力学均符合Freundlich和Langmuir等温方程式。(6)取华阴农场水样作为试验用水，通过提出的臭氧―砂碳―锰砂组合工艺，获得
了降低微污染水超标组份的最佳工艺：臭氧投加量2.0mg/L、时间20min，经臭氧化后的原水分别以0.6m/h和0.3m/h的速度，依次通过柱内径Ф100mm、高1000mm的分别装有20cm石英砂+25cm活性碳、20cm改性锰砂有机玻璃柱，最终滤液微污染成分浊度为0.2NTU、色度为1度，锰离子含量为0.060mg/L，处理的试验用水超标组分满足III类饮用水水源标准。
The Erhua district, including Hua county and Huayin city, is located in the low-lying area between the piedmont of Qinling Mountain and the downstream of Wei River. It's groundwater is recharged by water from the piedmont of Qinling Mountain and Wei River, so the groundwater quality is not good and the chemical composition is complex. The productsion and domestic water consumption in Erhua district was pumped from10m～30m shallow groundwater without any kind of treatment. Based on the project Water Quality Evolution Characteristic in Riverside Water Source Region Reach of Wei River, The theories and methods of hydrogeochemistry, hydrogeology, isotope chemistry and physical chemistry were applied to study the hydrochemical characteristics of shallow groundwater, water cycle rule, evolution mechanism and the effects of Wei River on groundwater quality. Furthermore, on account of the main exceeded micro-pollutants in shallow groundwater, the ozone-sand, carbon layer-manganese sand layer technological process were applied for the first time for the experiment researches, and the optimal technological condition of this process was gained based on theses experiments. The research results can provide the scientific base for the safe, clean water resource consumption and reasonable water resource exploitation.
Therefore, it has a significant theory and practice meaning for local groundwater evaluation, reasonable exploitation and drinking and production water safety to study the shallow groundwater cycle rules, analysis its hydrochemical characteristics and seek an appropriate treatment technological process. The main research conclusions are as follows:
(1) The distribution characteristics of hydrochemical types, mineralization and hardness of shallow groundwater in research area are:
From south to north, that is from the piedmont of Qinling Mountain to Wei River, the hydrochemical types are from simple to complex, namely, from HCO3·SO4-Ca-Mg to SO4·HCO3-Na-Ca, and then SO4·Cl-Na; from west to east, the changes of hydrochemical types are not significant, the hydrochemical types were HCO4·SO4-Ca-Mg and HCO3·SO4-Ca-Mg-Na near the piedmont of Qinling Mountain, SO4-Na and SO4-HCO3-Na-Ca near Wei River.
The total dissolved solids (TDS) were high in Xiamiao Street, Wangsu and Huaying farm along the Wei Rive and the mineralization there were high, too, so there were brackish water distribution areas. On the contrary, the TDS were low near the piedmont of Qinling Mountain and in the central of the research area, where were freshwater distribution areas.
The water hardness was generally high in research area, where Xiamiao Street, Huaying farm, Qilian and Fushui were extreme hard water distribution areas. In general, from south to north, water quality changes from hard water to extreme hard water.
(2) The ions molar concentration ratio of shallow groundwater, such as γci-/γCa2+, γNa+/γ Mg2+, γCl-/γSO42-and γci-/γHCO3-,showed that the hydrodynamic conditions became weaker and weaker from west to east, but stronger along the Wei River. The variations of the TDS and Na+content are more or less the same, namely where the TDS was high, where the Na+was in dominant. Moreover, the cumulative process of the soluble salt happened from south to north; meanwhile, water salinization had the same trend.
(3) The value of δ18O and δD in shallow groundwater and Wei River showed that the main recharge of Wei River and shallow groundwater near the piedmont of Qinling Mountain was precipitation. The distribution regularity of δ18O、δD in shallow groundwater crosswise (from west to east) and lengthwise (from south to north) reflected the runoff rules, namely the flow run from the piedmont of Qinling Mountain to bank of Wei River. There are groundwater depression cones in Wangsu Xiamiao Street and Huaying farm along the Wei River, to where Wei River recharge. Duancun Street is abundance with surface water, so surface water recharge groundwater.
(4) The variable fuzzy set theory was applied to evaluate water quality in research area, according to Groundwater Quality Standards (GB/T14848-1993), class IV water account for64%. From south to north (i.e. from the piedmont of Qinling Mountain to bank of Wei River), the water quality class of shallow groundwater was from II to IV, the water quality became worse and worse. From west to east, the variation of water quality was not significant, the class of water was IV in general. The water quality in Wei River was the same with that of riverside, but worse than shallow groundwater in riverside.
(5) The turbidity, chrominance and manganese ion exceeded in research area, the ozone-sand, carbon layer-manganese sand layer technological process wree applied for light polluted water treatment. The result showed that the oxidation on Ozone stage remove 80.0%and17.7%of chrominance and manganese, respectively. The turbidity and chrominance were reduced by sand, carbon layer, resulting class I of drinking water standard. The manganese sand layer which is improved by potassium permanganate can remove manganese to the Class II-III of drinking water standard and its manganese absorption kinetics model matches primary adsorption and Elovich equation, as well as Freundlich and Langmuir isotherm equation.
(6) The water from Huaying farm as test water was collected and gained the optimum technological conditions for reducing pollution indicators by means of the ozone-sand, carbon layer-manganese sand layer technological process. The ozone dosage is2.0mg/L for20min, then let the ozonized water go through the plexiglass columns at the speed of0.6m/h and0.3m/h, while the plexiglass columns was100mm in diameter,1000mm in tall and filled with20cm+25cm sand carbon and20cm improved manganese sand. The turbidity, chrominance and manganese content of final filtrate were0.2NTU, degree1and0.060mg/L, respectively. Treated water satisfied Class III of drinking water standards.
研究“二华”地区浅层地下水水循环规律，揭示其水化学特征，寻求适合该地区微污染浅层地下水处理工艺，对当地地下水水资源评价、合理开发利用以及居民生活、生产用水安全都具有重要的理论和生产实际意义。本文主要研究结论如下：
(1)研究区浅层地下水水化学类型、矿化度及硬度分布特征为：
由南向北，即从秦岭北麓到渭河沿岸，水化学类型由简单到复杂，主要从HCO_3·SO_4-Ca·Mg经SO_4·HCO_~(3-)Na·Ca过渡到SO_4·Cl-Na型；由西向东，即沿渭河流向，水化学类型变化不大，靠近秦岭山前，水化学类型以HCO_3·SO_4-Ca·Mg和HCO_3·SO_4-Ca·Mg·Na型为主，靠近渭河，水化学类型以SO_4·Cl-Na和SO_4·HCO_~(3-)Na·Ca型为主。
研究区渭河沿岸下庙街、王宿、华阴农场一带总溶解固体(TDS)较大，水质矿化度较高，为微咸水分布区；靠近秦岭山前、研究区中部TDS较小，为淡水分布区。
研究区地下水硬度普遍偏大，其中以下庙街、华阴农场、七连、夫水一带为极硬水分布区，整体上从南向北，水质从硬水过渡到极硬水。
(2)离子摩尔浓度比值γCl-/γCa~(2+)、γNa~+/γMg~(2+)、γCl-/γSO_4~(2-)和γCl-/γHCO_~(3-)表明：研究区靠近秦岭山前由西向东水动力条件逐渐较弱，渭河沿岸，水动力条件逐渐较强；TDS与Na~+变化一致，即TDS高的地方，Na~+离子的含量占优势；研究区由南向北方向上呈易溶盐的累积过程，水质总体向咸化方向发展。(3)针对研究区水文地质参数较少的原因，应用同位素δ18O、δD值分析研究区浅
层地下水水循环规律，研究表明：研究区在靠近秦岭山前的浅层地下水主要补给源为大气降水；研究区横向由西向东、纵向由南向北路径上浅层地下水的δ18O、δD分布规律反应了其径流规律：即径流由南向北，渭河沿岸地区王宿、下庙街、华阴农场一带存在地下水漏斗区，渭河河水侧向补给该区域；段村街一带，由于该区域地表水丰富，浅层地下水接受地表水的补给。
(4)采用可变模糊集理论评价了研究区水质，根据《地下水质量标准》(GB/T14848-1993)，IV类水质水占总评价水质的64.0%。研究区由南向北，浅层地下水水质类别由II类过渡到IV类，水质逐渐变差；由西向东，水质类别变化不大，基本为IV类；渭河水质与其沿岸浅层地下水水质属相同类别，但是，渭河河水水质要劣于沿岸浅层地下水水质。
(5)针对研究区水质属微污染水，水质主要超标指标为浊度、色度、金属离子锰，提出将臭氧―砂碳―锰砂组合工艺作为对微污染试验用水的处理流程，结果表明：臭氧阶段的氧化作用，对微污染水中的色度、锰离子的去除率为80.0%和17.7%；砂碳层将浊度、色度进一步降低，达到了I类饮用水水源标准；经过高锰酸钾改性的锰砂层，对锰离子去除后，水质达到II类～III类饮用水水源标准，其对锰离子吸附动力学模型符合一级吸附式和Elovich方程，吸附热力学均符合Freundlich和Langmuir等温方程式。(6)取华阴农场水样作为试验用水，通过提出的臭氧―砂碳―锰砂组合工艺，获得
了降低微污染水超标组份的最佳工艺：臭氧投加量2.0mg/L、时间20min，经臭氧化后的原水分别以0.6m/h和0.3m/h的速度，依次通过柱内径Ф100mm、高1000mm的分别装有20cm石英砂+25cm活性碳、20cm改性锰砂有机玻璃柱，最终滤液微污染成分浊度为0.2NTU、色度为1度，锰离子含量为0.060mg/L，处理的试验用水超标组分满足III类饮用水水源标准。
The Erhua district, including Hua county and Huayin city, is located in the low-lying area between the piedmont of Qinling Mountain and the downstream of Wei River. It's groundwater is recharged by water from the piedmont of Qinling Mountain and Wei River, so the groundwater quality is not good and the chemical composition is complex. The productsion and domestic water consumption in Erhua district was pumped from10m～30m shallow groundwater without any kind of treatment. Based on the project Water Quality Evolution Characteristic in Riverside Water Source Region Reach of Wei River, The theories and methods of hydrogeochemistry, hydrogeology, isotope chemistry and physical chemistry were applied to study the hydrochemical characteristics of shallow groundwater, water cycle rule, evolution mechanism and the effects of Wei River on groundwater quality. Furthermore, on account of the main exceeded micro-pollutants in shallow groundwater, the ozone-sand, carbon layer-manganese sand layer technological process were applied for the first time for the experiment researches, and the optimal technological condition of this process was gained based on theses experiments. The research results can provide the scientific base for the safe, clean water resource consumption and reasonable water resource exploitation.
Therefore, it has a significant theory and practice meaning for local groundwater evaluation, reasonable exploitation and drinking and production water safety to study the shallow groundwater cycle rules, analysis its hydrochemical characteristics and seek an appropriate treatment technological process. The main research conclusions are as follows:
(1) The distribution characteristics of hydrochemical types, mineralization and hardness of shallow groundwater in research area are:
From south to north, that is from the piedmont of Qinling Mountain to Wei River, the hydrochemical types are from simple to complex, namely, from HCO3·SO4-Ca-Mg to SO4·HCO3-Na-Ca, and then SO4·Cl-Na; from west to east, the changes of hydrochemical types are not significant, the hydrochemical types were HCO4·SO4-Ca-Mg and HCO3·SO4-Ca-Mg-Na near the piedmont of Qinling Mountain, SO4-Na and SO4-HCO3-Na-Ca near Wei River.
The total dissolved solids (TDS) were high in Xiamiao Street, Wangsu and Huaying farm along the Wei Rive and the mineralization there were high, too, so there were brackish water distribution areas. On the contrary, the TDS were low near the piedmont of Qinling Mountain and in the central of the research area, where were freshwater distribution areas.
The water hardness was generally high in research area, where Xiamiao Street, Huaying farm, Qilian and Fushui were extreme hard water distribution areas. In general, from south to north, water quality changes from hard water to extreme hard water.
(2) The ions molar concentration ratio of shallow groundwater, such as γci-/γCa2+, γNa+/γ Mg2+, γCl-/γSO42-and γci-/γHCO3-,showed that the hydrodynamic conditions became weaker and weaker from west to east, but stronger along the Wei River. The variations of the TDS and Na+content are more or less the same, namely where the TDS was high, where the Na+was in dominant. Moreover, the cumulative process of the soluble salt happened from south to north; meanwhile, water salinization had the same trend.
(3) The value of δ18O and δD in shallow groundwater and Wei River showed that the main recharge of Wei River and shallow groundwater near the piedmont of Qinling Mountain was precipitation. The distribution regularity of δ18O、δD in shallow groundwater crosswise (from west to east) and lengthwise (from south to north) reflected the runoff rules, namely the flow run from the piedmont of Qinling Mountain to bank of Wei River. There are groundwater depression cones in Wangsu Xiamiao Street and Huaying farm along the Wei River, to where Wei River recharge. Duancun Street is abundance with surface water, so surface water recharge groundwater.
(4) The variable fuzzy set theory was applied to evaluate water quality in research area, according to Groundwater Quality Standards (GB/T14848-1993), class IV water account for64%. From south to north (i.e. from the piedmont of Qinling Mountain to bank of Wei River), the water quality class of shallow groundwater was from II to IV, the water quality became worse and worse. From west to east, the variation of water quality was not significant, the class of water was IV in general. The water quality in Wei River was the same with that of riverside, but worse than shallow groundwater in riverside.
(5) The turbidity, chrominance and manganese ion exceeded in research area, the ozone-sand, carbon layer-manganese sand layer technological process wree applied for light polluted water treatment. The result showed that the oxidation on Ozone stage remove 80.0%and17.7%of chrominance and manganese, respectively. The turbidity and chrominance were reduced by sand, carbon layer, resulting class I of drinking water standard. The manganese sand layer which is improved by potassium permanganate can remove manganese to the Class II-III of drinking water standard and its manganese absorption kinetics model matches primary adsorption and Elovich equation, as well as Freundlich and Langmuir isotherm equation.
(6) The water from Huaying farm as test water was collected and gained the optimum technological conditions for reducing pollution indicators by means of the ozone-sand, carbon layer-manganese sand layer technological process. The ozone dosage is2.0mg/L for20min, then let the ozonized water go through the plexiglass columns at the speed of0.6m/h and0.3m/h, while the plexiglass columns was100mm in diameter,1000mm in tall and filled with20cm+25cm sand carbon and20cm improved manganese sand. The turbidity, chrominance and manganese content of final filtrate were0.2NTU, degree1and0.060mg/L, respectively. Treated water satisfied Class III of drinking water standards.
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