内蒙古河套平原高砷地下水水化学演化过程
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摘要
河套盆地位于内蒙古自治区中西部，是我国饮水型地方性砷中毒暴露面积最大、受影响人口最多的地区。原生高砷地下水导致的砷中毒对居民身体健康造成了严重的影响，部分中毒者失去劳动能力，严重者甚至导致死亡。地方性砷中毒严重制约着当地的经济和社会的发展。因而，尽量避免饮用高砷水，保障当地居民饮用水安全有着非常重要的意义。
本文通过对研究区大范围的地下水采样分析，对区内地下水的砷分布和水化学特征有了比较清楚的认识。高砷地下水的主要特征与世界其他高砷区相似，即具有较高的pH，较强的还原环境，铁、锰含量较高，SO_4~(2-)和NO3-被还原而浓度较低，水中砷以As（Ⅲ）为主。除此之外，该区另一显著的特点是，高氟伴随着高砷地下水同时出现，这在其他高砷区并未发现。
在还原强度的分析上，本文打破原有的简单靠氧化还原电位或还原产物如硫化物或氨氮的方式定性说明还原强度，而是通过类比方法计算SO_4~(2-)的还原量及还原比率，定量的说明还原强度与砷含量的关系。
与此同时，在研究区选择典型剖面，钻孔采集沉积物分析矿物成分及组成，并在不同层次含水层成井，定期采集不同深度含水层水样，分析沉积物中矿物与地下水之间的水岩作用，在时间和空间上对水中砷和氟含量的影响发现：（1）砷与氟均来自于含水层沉积矿物中，但经过分析发现，两者的水文地球化学过程是不同的。砷通过还原作用进入地下水中，在迁移过程中受到蒸发浓缩作用和解吸附作用的影响。砷浓度随着地下水水位的周期性变化也发生周期性起伏，且随着浅层地下水水位的升高而增加。而氟在深度上并未表现出明显的变化，主要受蒸发浓缩作用影响，使得地下水中Ca~(2+)与HCO3-沉淀，萤石加速溶解于地下水中，水中氟含量升高；（2）山前地下水灌溉区，由于灌溉期抽取地下水，使得地下水位下降，含水介质氧化还原环境发生改变，降低了砷由沉积物向地下水中释放，而非灌溉期地下水位升高使得含水介质恢复还原环境，地下水中砷含量升高；引黄灌溉区域，由于地表水对地下水的补给，地下水水位升高，开始阶段由于稀释作用使得氟和砷含量降低，到夏季受蒸发浓缩作用影响，氟含量升高。而砷含量升高的原因是由于沉积层氧化还原环境发生改变，加快了沉积物中砷向地下水中释放的速度。上层地下水受到的影响大于下层，由于存在滞后效应，下层地下水受影响时间晚于上层;（3）S2-, NH_3~-N和Fe~(2+)三种还原性产物与砷呈现出较好的相关关系，进一步证明了砷的释放与还原环境有关。
The Hetao basin is located in the Midwestern part of Mongolia, where high Asgroundwater seriously affected health of local residents. Many people suffered fromendemic arsenicosis. Some lost the ability of working, and some faced death. Arsenicpoisoning has limited the development of local economy and the society. Thus, it isvery important to avoid drinking high-arsenic water in order to protect the drinkingwater safety for local residents.
According to three-year investigation of the groundwater samples, thedistribution of high As groundwater and their geochemical characteristics have beenfigured out. The high As groundwater was characterised by high pH, low redoxpotential and the high concentrations of Fe and Mn. Concentrations of SO_4~(2-)and NO3-were relatively low because of reduced conditions. Arsenic(III) was the predominantAs species in high As groundwater. Besides, high F concentration was also observedin high As groundwater, which was not found in other high As groundwater areas.
Although Eh, sulfide or ammonia was normally used to correlate with Asconcentrations, they are only indicators for low redox potentials and can not be usedfor quantatively describing As mobilization in the aquifers, The quantitativerelationship between the reducing intensity of SO_4~(2-)and As concentrations in thegroundwaters was established.
A typical flow path was selected in the study area to study the spatial andtemporal evolution of high-arsenic groundwater. Sediments were collected from thedrilling boreholes and analyzed for chemical components. Long-term monitoring dataof multilevel samples at four locations were used to evaluate the influence ofwater-rock interaction on the concentration of As. Both groundwater As and F comefrom the aquifer sediment. Hydrogeochemical processes of these two elements weredifferent. Arsenic was mobilized into groundwater in reduction conditions, andconcentrated because of the evaporation and concentration effect and desorption.Besides, As concentrations varied with fluctuations of groundwater levels, which washigher with high groundwater levels. However, F-concentration was affected by theevaporation and mineral precipitation. Low Ca2+concentrations led to high F-concentration.
In groundwater irrigation areas, the extraction of groundwater resulted inchanges of redox conditions and adsorption of As from groundwater to sediments.During the seasons without irrigation, the groundwater level increased leading to lowredox potential, whern As concentrations increased. In the surface water Irrigationareas, the groundwater level increased because of the recharge from surface water,which makes fluoride and arsenic concentrations decreased in the sallowest aquifers. In summer, the fluoride concentration increased due to the evaporation. However, theelevated levels of arsenic results from the change of redox conditions whichaccelerates the speed of arsenic release to groundwater. The impact of groundwater bythe upper aquifers is greater than lower ones. Concentrations of S2-, NH3-N and Fe2+showed good correlations with As, which further proves the correlation between theredox environment and the release of As.
本文通过对研究区大范围的地下水采样分析，对区内地下水的砷分布和水化学特征有了比较清楚的认识。高砷地下水的主要特征与世界其他高砷区相似，即具有较高的pH，较强的还原环境，铁、锰含量较高，SO_4~(2-)和NO3-被还原而浓度较低，水中砷以As（Ⅲ）为主。除此之外，该区另一显著的特点是，高氟伴随着高砷地下水同时出现，这在其他高砷区并未发现。
在还原强度的分析上，本文打破原有的简单靠氧化还原电位或还原产物如硫化物或氨氮的方式定性说明还原强度，而是通过类比方法计算SO_4~(2-)的还原量及还原比率，定量的说明还原强度与砷含量的关系。
与此同时，在研究区选择典型剖面，钻孔采集沉积物分析矿物成分及组成，并在不同层次含水层成井，定期采集不同深度含水层水样，分析沉积物中矿物与地下水之间的水岩作用，在时间和空间上对水中砷和氟含量的影响发现：（1）砷与氟均来自于含水层沉积矿物中，但经过分析发现，两者的水文地球化学过程是不同的。砷通过还原作用进入地下水中，在迁移过程中受到蒸发浓缩作用和解吸附作用的影响。砷浓度随着地下水水位的周期性变化也发生周期性起伏，且随着浅层地下水水位的升高而增加。而氟在深度上并未表现出明显的变化，主要受蒸发浓缩作用影响，使得地下水中Ca~(2+)与HCO3-沉淀，萤石加速溶解于地下水中，水中氟含量升高；（2）山前地下水灌溉区，由于灌溉期抽取地下水，使得地下水位下降，含水介质氧化还原环境发生改变，降低了砷由沉积物向地下水中释放，而非灌溉期地下水位升高使得含水介质恢复还原环境，地下水中砷含量升高；引黄灌溉区域，由于地表水对地下水的补给，地下水水位升高，开始阶段由于稀释作用使得氟和砷含量降低，到夏季受蒸发浓缩作用影响，氟含量升高。而砷含量升高的原因是由于沉积层氧化还原环境发生改变，加快了沉积物中砷向地下水中释放的速度。上层地下水受到的影响大于下层，由于存在滞后效应，下层地下水受影响时间晚于上层;（3）S2-, NH_3~-N和Fe~(2+)三种还原性产物与砷呈现出较好的相关关系，进一步证明了砷的释放与还原环境有关。
The Hetao basin is located in the Midwestern part of Mongolia, where high Asgroundwater seriously affected health of local residents. Many people suffered fromendemic arsenicosis. Some lost the ability of working, and some faced death. Arsenicpoisoning has limited the development of local economy and the society. Thus, it isvery important to avoid drinking high-arsenic water in order to protect the drinkingwater safety for local residents.
According to three-year investigation of the groundwater samples, thedistribution of high As groundwater and their geochemical characteristics have beenfigured out. The high As groundwater was characterised by high pH, low redoxpotential and the high concentrations of Fe and Mn. Concentrations of SO_4~(2-)and NO3-were relatively low because of reduced conditions. Arsenic(III) was the predominantAs species in high As groundwater. Besides, high F concentration was also observedin high As groundwater, which was not found in other high As groundwater areas.
Although Eh, sulfide or ammonia was normally used to correlate with Asconcentrations, they are only indicators for low redox potentials and can not be usedfor quantatively describing As mobilization in the aquifers, The quantitativerelationship between the reducing intensity of SO_4~(2-)and As concentrations in thegroundwaters was established.
A typical flow path was selected in the study area to study the spatial andtemporal evolution of high-arsenic groundwater. Sediments were collected from thedrilling boreholes and analyzed for chemical components. Long-term monitoring dataof multilevel samples at four locations were used to evaluate the influence ofwater-rock interaction on the concentration of As. Both groundwater As and F comefrom the aquifer sediment. Hydrogeochemical processes of these two elements weredifferent. Arsenic was mobilized into groundwater in reduction conditions, andconcentrated because of the evaporation and concentration effect and desorption.Besides, As concentrations varied with fluctuations of groundwater levels, which washigher with high groundwater levels. However, F-concentration was affected by theevaporation and mineral precipitation. Low Ca2+concentrations led to high F-concentration.
In groundwater irrigation areas, the extraction of groundwater resulted inchanges of redox conditions and adsorption of As from groundwater to sediments.During the seasons without irrigation, the groundwater level increased leading to lowredox potential, whern As concentrations increased. In the surface water Irrigationareas, the groundwater level increased because of the recharge from surface water,which makes fluoride and arsenic concentrations decreased in the sallowest aquifers. In summer, the fluoride concentration increased due to the evaporation. However, theelevated levels of arsenic results from the change of redox conditions whichaccelerates the speed of arsenic release to groundwater. The impact of groundwater bythe upper aquifers is greater than lower ones. Concentrations of S2-, NH3-N and Fe2+showed good correlations with As, which further proves the correlation between theredox environment and the release of As.
引文
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