Distribution Characteristics of Dissolved Manganese in the Lateral Hyporheic Zone between River and Groundwater in the Lower Reaches of the Han River
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摘要: 江汉平原浅层地下水中锰含量普遍较高，探究锰在河流交互带中的分布特征有助于认识交互带中锰的生物地球化学过程，对水质的保护具有重要指导意义.通过监测汉江下游侧向交互带河水、地下水中溶解态锰含量及其相关指标，分析不同河水-地下水交互作用方向下溶解态锰的时空分布规律，并探讨其成因.结果表明：研究区侧向交互带中靠近河岸带区域存在溶解态锰的富集，且在有局部反向流的地方锰含量较高；该局部富集的现象在河水补给地下水的交互带中更加明显；泄洪后该富集区域随水流方向发生迁移；研究区地下水中锰的含量与HCO3-、Ca2+、Mg2+呈极显著正相关，与NO3-、Fe2+显著负相关，但与交互带地下水中Eh和pH不相关.交互带溶解态锰的时空分布受地形条件、水动力和水化学的共同影响.Abstract: The content of manganese in shallow groundwater in Jianghan Plain is generally high. Studying the distribution characteristics of manganese in the hyporheic zone helps to understand manganese's biogeochemical process in the hyporheic zone. It is of great significance for guiding the protection of river and groundwater quality. This study takes the lateral hyporheic zone in the Han River's lower reaches as the research object. The temporal and spatial distribution of dissolved manganese under different interaction directions between river and groundwater in the lateral hyporheic zone is studied and discussed by detecting manganese concentration and its related parameters in the river and groundwater. The results showed that the dissolved manganese is enriched in the river-groundwater lateral interaction zone near the riparian zone, and the manganese content is higher in the place where there is local reverse flow; The phenomenon of local enrichment is more obvious in the interactive zone where river water supplies groundwater. After flooding for 1-3 months, the enrichment area migrates with the direction of water flow; The dissolved manganese concentration in the groundwater of the study area has a very significant positive correlation with HCO3-, Mg2+, Ca2+, and has a remarkably substantial negative correlation with NO3-. It is also negatively correlated with Fe2+. However, it is not related to the Eh and pH of groundwater in the hyporheic zone.In a word, the spatial and temporal distribution of dissolved manganese in the hyporheic zone is influenced by topographic conditions, hydrodynamics and hydrochemistry.
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图 1 研究区及采样点分布
右图蓝色分别代表河水和地下水水位，红色线段为多水平监测井的位置及高程
Fig. 1. Distribution map of the study area and sampling points
图 2 PM01河水与交互带地下水的水位、水流场及溶解态锰的时空分布
图中白色箭头的朝向和长度分别指示水流的方向和流速大小；空心圆为采样点，其中横坐标为0的点位样品为各剖面对应的河水样品
Fig. 2. The water level, flow field, and time-space distribution of dissolved Mn in profile 1 of the hyporheic zone
图 3 PM02河水与交互带地下水的水位、水流场及溶解态锰的时空分布
图中标识同图 2
Fig. 3. The water level, flow field, and time-space distribution of dissolved Mn in profile 2 of the hyporheic zone
图 4 PM03河水与交互带地下水的水位、水流场及溶解态锰的时空分布
图中标识同图 2
Fig. 4. The water level, flow field, and time-space distribution of dissolved Mn in profile 3 of the hyporheic zone
图 5 研究区地下水化学指标聚类分析树状图
Fig. 5. Cluster analysis dendrogram of groundwater chemical parameters in the study area
图 6 标准状态下研究区Mn与C、N和水环境Eh-pH相图
黑色圆点为样品点
Fig. 6. Phase diagram of Mn, C, N and water environment Eh-pH in the study area under standard conditions
图 7 不同氧化还原对的电极电势以及成岩孔隙水中相应各组分浓度随深度变化图
引自Froelich et al.（1979）；Lam and Kuypers（2011）；董志国等（2020）
Fig. 7. The electrode potential of different redox pairs and the corresponding component concentrations in diagenetic pore water vary with depth
表 1 水样不同指标的前处理及保存方法
Table 1. Pretreatment and preservation methods of different indexes of water samples
水质指标 处理方法 保存和测试 Mn 水样过滤(0.45 μm) 后酸化(1+1 HNO3) 避光，高碘酸钾显色法现场测试 Fe 水样过滤(0.45 μm) 后酸化(1+3 HCl) 避光，邻菲罗啉显色法现场测试 HCO3- 水样过滤(0.45 μm) 现场滴定测定 pH、Eh、DO 通入过渡仓隔绝空气 水质分析仪现场测定 DOC 水样过滤(0.45 μm)后酸化(H2SO4) 避光，低温保存，带回上机测试 阴阳离子 水样过滤(0.45 μm)后加保护剂保存 避光，低温保存，带回上机测试 注：锰和铁取样过程尽量保证隔绝氧气，因此采用注射器外接滤头的方式，直接将抽出的地下水过滤后酸化保存. 
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表 2 研究区河水-地下水化学组分（单位：mg/L，pH和Eh除外）
Table 2. Chemical composition of river water and groundwater in the study area(unit: mg/L, except pH and Eh)
化学组分 河水 地下水 最大值 最小值 平均值 变异系数 最大值 最小值 平均值 变异系数 Mn2+ 0.77 0.00 0.20 1.26 6.61 0.00 2.29 0.75 pH 8.56 6.96 7.95 0.04 8.01 6.11 7.01 0.04 DO 11.85 3.20 8.17 0.32 2.55 0.00 0.41 1.14 Eh (mV) 341.60 -1.30 115.22 0.77 315.00 -392.30 -85.88 -1.33 Fe2+ 0.45 0.00 0.14 1.08 35.41 0.00 3.88 1.89 DOC 6.67 2.41 3.59 0.31 22.50 0.55 2.77 0.80 HCO3- 436.90 57.97 193.09 0.57 1 032.46 100.68 498.82 0.34 Cl- 18.28 1.46 8.75 0.46 153.70 0.49 12.81 1.24 NO3- 10.88 0.00 3.08 0.98 47.63 0.00 1.76 3.54 SO42- 85.19 0.00 28.41 0.62 335.21 0.00 31.73 1.15 K+ 3.43 0.05 1.77 0.54 5.32 0.00 1.67 0.69 Ca2+ 104.33 0.05 48.60 0.52 303.62 12.91 113.01 0.47 Na+ 13.99 5.87 10.09 0.22 22.51 0.00 8.17 0.35 Mg2+ 23.38 0.00 11.49 0.49 54.45 0.00 23.86 0.34
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表 3 研究地下水水化学指标相关系数表
Table 3. The correlation coefficient table of groundwater hydrochemical indicators in the study area
pH DO Ec Eh DOC HCO3- Cl- NO3- SO42- K+ Ca2+ Na+ Mg2+ Fe2+ Mn2+ -0.082 -0.023 0.089 -0.076 -0.076 0.276** -0.194** -0.248** -0.062 0.218** 0.135** 0.066 0.364** -0.115* HCO3-- -0.538** -0.147** 0.420** -0.085 0.151** 1 0.154** 0.127* -0.181** 0.070 0.511** -0.110* 0.756** 0.379** DOC 0.001 0.213** 0.198** 0.005 1 0.151** 0.125* 0.009 -0.156** 0.273** 0.198** 0.111* 0.083 0.330** 注：**. 在0.01级别（双尾），相关性显著；*. 在0.05级别（双尾），相关性显著.
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