海河流域大清河平原区地下水化学特征及演化规律分析

孟瑞芳; 杨会峰; 白华; 徐步云

doi:10.15898/j.cnki.11-2131/td.202207010121

海河流域大清河平原区地下水化学特征及演化规律分析

孟瑞芳^{1, 2,},
杨会峰^{1, 2, ,},
白华^{1, 2},
徐步云¹

1.
中国地质科学院水文地质环境地质研究所，河北石家庄 050061
2.
河北沧州平原区地下水与地面沉降国家野外科学观测研究站，河北石家庄 050061

基金项目:

国家自然科学基金地质联合基金 U2244214

中国地质调查局地质调查项目 DD20190336

中国地质调查局地质调查项目 DD2022175

中国地质科学院基本科研业务费项目 SK202118

中国地质科学院基本科研业务费项目 SK202216

河北省创新能力提升计划高水平人才团队建设专项 225A4204D

详细信息

作者简介:
孟瑞芳，硕士，副研究员，主要从事水文地质与水循环研究工作。E-mail: 631216332@163.com

通讯作者:
杨会峰，博士，研究员，主要从事水文地质与水循环研究工作。E-mail: yanghuifeng@mail.cgs.gov.cn

中图分类号: P641.12;P332.7
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出版历程
- 收稿日期: 2022-06-30
- 修回日期: 2022-08-15
- 录用日期: 2022-11-04
- 网络出版日期: 2023-02-01
- 刊出日期: 2023-03-27

Chemical Characteristics and Evolutionary Patterns of Groundwater in the Daqing River Plain Area of Haihe Basin

MENG Ruifang^{1, 2,},
YANG Huifeng^{1, 2, ,},
BAI Hua^{1, 2},
XU Buyun¹

1.
Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences, Shijiazhuang 050061, China
2.
National Field Scientific Observation and Research Station on Groundwater and Ground Subsidence in the Plain Area of Cangzhou, Shijiazhuang 050061, China

摘要

摘要:
地下水超采引发大清河流域范围内一系列生态环境负效应，地下水与地表水关系密切，厘清大清河流域平原区地下水化学特征及演化规律，对大清河流域水资源合理开发利用具有重要意义，然而目前尚缺乏对大清河流域地下水化学特征特别是其历史以来的演变规律作系统的分析。本文以海河流域大清河平原区地下含水系统为例，采集浅层含水层组47个水样和深层含水层组32个水样，测试了主要阴离子(Cl^-、SO₄^2-、NO₃^-)和阳离子(K⁺、Na⁺、Ca²⁺、Mg²⁺)等指标，利用水化学类型、吉布斯模型、离子比值关系等方法，研究其水化学特征及演化规律。测试结果显示：浅层含水层组受到气象和人为因素影响较大，浅层和深层含水层组pH值(7.35~8.92)差异不大，偏碱性；浅层含水层组由于农业活动等影响，造成局部地区的硝酸盐和硫酸盐污染。水岩相互作用分析显示：硅酸盐矿物风化是研究区主要的矿物来源，硅酸盐矿物溶解、阳离子交换为主要的水化学作用。研究区浅层地下水水化学特征总体上受地形和水文地质条件的影响，由山前平原-中部平原呈规律性分布。现状地下水化学类型为沿地下水径流方向由山前的HCO₃-Ca·Mg(Ca)型，经HCO₃-Mg·Ca、HCO₃-Mg·Ca·Na、HCO₃-Na·Mg·Ca向HCO₃·Cl-Na·Ca、HCO₃·Cl·SO₄-Na至平原中部冲湖积平原的Cl(SO₄)-Na转变。水化学演变分析显示中部平原地下水由以Cl·HCO₃-Ca·Na、HCO₃·Cl-Ca·Na型为主，转变为当前条件下以Cl·HCO₃-Ca·Na、SO₄·Cl-Na·Mg型为主。总体上，研究区现状水化学类型复杂多样，且分布上虽然仍受地形与地质条件的控制，但越来越多地受到以开采为主的人类活动的影响，应重视人类活动对该区域地下水的影响，合理布置开采方案。本文利用水化学方法研究了大清河流域平原区地下水化学特征及演化规律，厘清了大清河流域平原的水化学特征以及水化学类型演变规律，初步分析了演变趋势造成的原因，特别是指明地下水化学演变越来越受到人类活动的影响，后续将在水化学未来的演变预测上进行相关的研究。
- 大清河流域平原区 /
- 地下水水化学全分析 /
- 水化学类型 /
- 水化学演变 /
- 人类活动
要点
(1) 浅层含水层组TDS变化幅度大，深层含水层组TDS变化幅度小，浅层含水层组受到气象和人为因素影响较大。

(2) 硅酸盐矿物风化溶解、阳离子交换为主要的矿物来源和水化学作用。

(3) 浅层地下水化学特征总体上受地形和水文地质条件的影响，由山前平原-中部平原呈规律性分布。

(4) 研究区水化学类型复杂多样，且越来越多地受到以开采为主的人类活动的影响。

HIGHLIGHTS
(1) The TDS of the shallow aquifer groups varies greatly, while the TDS of the deep aquifer groups has a small variation. The shallow aquifer groups are more influenced by meteorological and anthropogenic factors.

(2) Weathering dissolution of silicate minerals and cation exchange are the main mineral sources and water chemistry.

(3) The chemical characteristics of shallow groundwater are generally influenced by the topography and hydrogeological conditions and are regularly distributed from the piedmont plain to the central plain.

(4) The current water chemistry types are complex and diverse and are increasingly influenced by human activities such as mining.
Abstract:
BACKGROUND
Groundwater is closely related to surface water. Groundwater over-extraction has triggered a series of negative ecological effects in the Daqing River basin. The evolution of groundwater chemical characteristics is influenced by both natural and anthropogenic factors. The analysis of groundwater chemical characteristics can indicate the meteorological-hydrological and water-rock interaction during groundwater runoff, thus reflecting the groundwater circulation path, groundwater system characteristics and evolution laws, etc. It also helps to monitor groundwater dynamics and prevent the occurrence of groundwater pollution.
OBJECTIVES
To clarify the chemical characteristics and evolution of groundwater in the plain area of the Daqing River basin, which will be important for the rational development and utilization of water resources in the basin.
METHODS
47 water samples from the shallow aquifer groups and 32 water samples from the deep aquifer groups were collected to analyze the main anions (Cl^-, SO₄^2-, NO₃^-) and cations (K⁺, Na⁺, Ca²⁺, Mg²⁺). The water chemistry characteristics and evolution laws were studied by using the water chemistry type, Gibbs model and ion ratio relationship. On-site portable water quality analyzer (HACH-HQ40d) was used to test pH (accuracy 0.01), total dissolved solids (TDS, accuracy 0.01) and other parameters, and groundwater samples were collected after the indicators were stabilized. All samples were sent to the laboratory at low temperature and stored in a refrigerator at 4℃, and groundwater alkalinity was determined by titration on the same day. Seven days later, the samples were sent to the Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences for testing of major anions (Cl^-, SO₄^2-, NO₃^-) and major cations (K⁺, Na⁺, Ca²⁺, Mg²⁺) using inductively coupled plasma-optical emission spectrometry (iCAP6300). The anion and cation charge balance error was less than 5%, and the anion and cation test accuracy was 0.01mg/L.
RESULTS
The test results showed that the largest deviation was in the water sample from Hanbao Village, Liu Lizhuang Town, Anxin County, Baoding City, Hebei Province, which was from the shallow aquifer groups, and the maximum TDS reached 6015.00mg/L. The TDS of the shallow aquifer groups ranged from 254.10 to 6015.00mg/L, with an average of 664.14mg/L, a large coefficient of variation and a large variation in TDS, indicating that the shallow aquifer groups were affected by meteorological and human factors. The TDS of the deep aquifer groups ranged from 197.10 to 691.40mg/L, with an average of 278.58mg/L, and the coefficient of variation was small, indicating that the groundwater of the deep aquifer groups was less affected by meteorological and human activities than that of the shallow aquifer groups. A small portion of the sampling points of the shallow aquifer groups in the area were brackish water and salt water. The TDS of the deep aquifer groups was generally less than 1000mg/L, which was suitable for use as a mining layer. The pH values of the shallow and deep aquifer groupss in the study area were not very different (7.35-8.92) and were alkaline. The NO₃^- maximum value of 298.40mg/L and SO₄^2-maximum value of 3091.00mg/L in the shallow aquifer groups, but the average value was not significant, indicating that the shallow aquifer groups have caused nitrate and sulfate pollution in local areas due to agricultural activities and other effects.

In the shallow layer of the study area, except for the difference in hydraulic conditions in the northern piedmont plain where flaky or spotty HCO₃-Cl-SO₄ and HCO₃-Cl type water occurred, the anions in most of the piedmont plain were mainly HCO₃ type, and the cations were mainly Ca and Ca-Mg and Mg-Ca. During the discharge of groundwater along the piedmont plain to the mouth of the alluvial fan, the cations changed from Ca-Mg type to Na type in order through Ca-Mg-Na, Na-Ca-Mg, Na-Mg-Ca, Na-Ca to Na type, and anions from HCO₃ type to SO₄ and Cl type via HCO₃-SO₄, HCO₃-SO₄-Cl, HCO₃-Cl-SO₄, SO₄-Cl. The deep groundwater cations were relatively more complex, and the zonation was more obvious: from the piedmont plain to the bottom of the alluvial fan, the cations transition from Ca, Ca-Mg, Mg-Ca, Na-Mg-Ca (Mg-Ca-Na) type to Na-Ca and Na type water.
The shallow aquifer groups were basically located in the area of water-rock interaction, and individual points showed some influence of evaporation concentration. The deep aquifer groups were subjected to water-rock interaction and less affected by evaporation and atmospheric precipitation. The analysis results showed that the milligram equivalent concentration ratio of (Ca²⁺+Mg²⁺)+(HCO₃^-+SO₄^2-) to Na⁺+K⁺-Cl^- was close to -1, indicating a more significant cation exchange effect. The groundwater samples in this study area were mostly distributed near the end elements of silicate minerals, indicating that weathering of silicate minerals (such as feldspar) was the main hydrogeochemical control factor in the study area, which was consistent with the lithological characteristics of aquifers in the groundwater of the Daqing River basin plain, and the test results also showed that HCO₃^- was the dominant ion in both shallow and deep aquifer groups.
The SI values of calcite in the shallow aquifer groups in this study area ranged from -0.46 to 1.35, dolomite SI values from -0.88 to 3.02, gypsum SI values from -3.1 to -0.68, and rock salt SI values from -8.53 to -4.75, indicating that calcite and dolomite were partially saturated and partially unsaturated, and both gypsum and rock salt were unsaturated. Cl^-/(Na⁺+K⁺) could determine whether the groundwater was influenced by the dissolution of silicate rock. Most of the groundwater samples in this study area exhibited Cl^-/(Na⁺+K⁺) < 1, indicating that, in addition to rock salt in dissolved state, silicate mineral dissolution (e.g., potassium feldspar and sodium feldspar) was the main source of excess Na⁺ and K⁺. The Na⁺ content may also originate from cation exchange, and the high Cl^-, the higher concentration may be the input of foreign contamination. The HCO₃^-/(Ca²⁺+Mg²⁺) of the samples from the shallow aquifer groups was basically less than 1, showing excess Ca²⁺ and Mg²⁺, suggesting other sources of Ca²⁺ or Mg²⁺, while the (HCO₃^-+SO₄^2-)/(Ca²⁺+Mg²⁺) of the shallow aquifer groups was distributed above and below the 1∶1 line on both sides, suggesting that evaporite minerals (e.g. gypsum) may also be an important source of Ca²⁺ for the shallow aquifer groups, as evidenced by the unsaturated state of gypsum in groundwater, in addition to the increase in SO₄^2- due to human activities. Both HCO₃^-/(Ca²⁺+Mg²⁺) and (HCO₃^-+SO₄^2-)/(Ca²⁺+Mg²⁺) of the deep aquifer groups lay above the 1∶1 line, and the excess HCO₃^- implied silicate dissolution dominance, or the presence of cation exchange, leading to a lower Ca²⁺ content. (Cl^-+SO₄^2-)/(HCO₃^-) could indicate the dissolution status of evaporites and carbonates, and water samples from shallow and deep aquifer groups were mainly distributed in the (Cl^-+SO₄^2-)/(HCO₃^-)=1∶1 line below, which indicated that its chemical components were more dissolved by carbonate rocks.
In the influence zone of the Caohe River in the northern part of Mancheng District, the water chemistry changed from HCO₃-Ca-Mg water to Cl-HCO₃-Ca-Na water; at the alluvial fan margin of Jiehe River in Shunping County and at the alluvial fan margin of Rejected Horse River in Zhuozhou City, the proportion of Na content in groundwater gradually exceeded that of Mg as the cation content second only to Ca, and the water chemistry changed from HCO₃-Ca-Mg water to HCO₃-Ca-Na-Mg type water. The groundwater in the central plain changed from Cl-HCO₃-Ca-Na and HCO₃-Cl-Ca-Na type water with island and strip distribution of SO₄-HCO₃-Na-Mg, SO₄-HCO₃-Na, SO₄-Na-Mg and HCO₃-Na-Mg type water to Cl-HCO₃-Ca-Na, SO₄-Cl-Na-Mg type water dominated and mingled with HCO₃-Cl-Ca-Mg, Cl-SO₄-Na-Mg, HCO₃-Cl-SO₄-Na, HCO₃-SO₄-Na, HCO₃-SO₄-Na, HCO₃-SO₄-Na-Mg, and Cl-SO₄-Na-Mg type water.
The average NO₃^- content of the shallow aquifer was 28.78mg/L, and the average NO₃^- content of the deep aquifer was 4.55mg/L, indicating that nitrate pollution was serious in the shallow groundwater local area of the study area. Referring to the groundwater quality standard (GB/T 14848—2017) for ClassⅢ water, there were 17 sampling points in the shallow aquifer groups with NO₃^- content over 20mg/L and 5 sampling points in the shallow aquifer groups with SO₄^2- greater than 250g/L, indicating that these sampling sites were affected by anthropogenic activities, resulting in nitrate and sulfate pollution. A ratio of SO₄^2-/Ca²⁺ to NO₃^-/Ca²⁺ greater than 1 indicated that industrial and mining activities had a greater impact on groundwater, and a ratio less than 1 was more disturbed by agricultural activities and residential sewage. The results showed that the ratio of the deep aquifer groups was greater than 1, and only the 240m well in the north of Erlangmiao Village, Dingzhou City, Baoding City, Hebei Province, was less than 1. This indicated that the deep aquifer groups were basically affected by industrial and mining activities, but not by agricultural activities and residential sewage. In the shallow aquifer groups, there were 27 water samples with SO₄^2--Ca²⁺ to NO₃-Ca²⁺ ratio greater than 1, and 20 water samples with SO₄^2--Ca²⁺ to NO₃^--Ca²⁺ ratio less than 1, indicating that the shallow aquifer groups were partly influenced by industrial and mining activities, and partly influenced by agricultural activities and domestic sewage of residents.
CONCLUSIONS
The characteristics and evolution of groundwater chemistry in the plain area of the Daqing River basin was investigated by using the water chemistry method, clarifying the characteristics of the water chemistry and the evolution of water chemistry types in the plain area of the Daqing River Basin. Reasons for the evolution trend were also investigated, indicating that the evolution of groundwater chemistry is increasingly influenced by human activities. Relevant research will be conducted on the prediction of the future evolution of water chemistry.
- plain area of Daqing River Basin /
- full analysis of groundwater water chemistry /
- water chemistry type /
- water chemistry evolution /
- human activity

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01 地球化学基准与环境监测实验室分析指标对比与建议

王学求^{1, 2}，张勤^{1, 2}，白金峰^{1, 2}，姚文生^{1, 2}，刘妹^{1, 2}，刘雪敏³，王玮^{1, 2}

(1.自然资源部地球化学探测重点实验室，中国地质科学院地球物理地球化学勘查研究所，河北廊坊 065000；2.联合国教科文组织全球尺度地球化学国际研究中心，河北廊坊 065000；3.成都理工大学，四川成都 610059)

全球变化是当今社会普遍关注的热点问题，自然和人为注入或导致的化学元素及其化合物再分配是引起全球变化的主导因素。要监控全球化学变化，特别是监控人类排放的重金属、放射性等注入量以及碳循环，首先要建立全球地球化学基准网，获得化学元素基准值和基准图，作为未来环境变化的定量参照标尺。全球代表性样品采集和实验室高质量分析数据是关键，环境变化量必须大于野外采样误差和实验室分析误差之和，才能鉴别环境变化。该文提出了实验室分析的6条基本准则，用于指导全球高质量和一致性地球化学数据的获取，拟为在地球化学基准网基础上，最终建成全球性地球化学观测网，持续监测全球化学变化奠定基础。

15 地质样品中贵金属元素的预处理方法研究进展

王烨，于亚辉^*，王琳，张明炜，黄杰，吴林海

(河南省岩石矿物测试中心国土资源部贵金属分析与勘查技术重点实验室，河南郑州 450012)

贵金属已被全球许多国家列为战略性关键矿产资源，受到了严格控制、管理及储备。而贵金属元素在地壳中的含量甚微，如金仅为15×10^-9，银为1×10^-7；对于铂族元素，即使是有价值的工业富集，其品位与金相当甚至更低，导致了贵金属的供需矛盾日渐突出。由于贵金属稀少及其重要的应用价值，建立准确测定痕量、超痕量贵金属元素的分析方法，对于贵金属矿产资源勘查、评价和合理开采具有重要的指导意义。贵金属分析作为地质样品分析中最困难的任务之一，已成为影响贵金属矿产资源勘查、评价及相关研究工作的瓶颈，也是长期以来地球化学家难以获得广泛认同的铂族元素地壳丰度值的重要原因。对于含有贵金属的地质样品，其组成十分复杂，贵金属元素的分解、分离富集则是关键的研究内容。目前，锡试金法、镍锍试金法是分解贵金属的主要技术手段，采用碲共沉淀法、吸附法等方法进行分离富集，结合高灵敏度的ICP-MS，可实现8个贵金属元素的同时分析测定。实际应用中，该文建议应针对不同类型地质样品的特点，选取适宜的分解及分离富集方法，并严格控制流程本底及各个环节污染问题，实现多技术、多方法联用，满足贵金属分析的要求。

30 特殊地质样品中钼同位素分析的化学前处理方法研究

闻静^{1, 2}，张羽旭^1*，温汉捷^{1, 2}，朱传威¹，樊海峰¹

(1.中国科学院地球化学研究所，矿床地球化学国家重点实验室，贵州贵阳 550081；2.中国科学院大学，北京 100049)

钼(Mo)是氧化还原敏感元素，其同位素分馏受氧化还原条件的控制，在不同的地质样品中有明显的同位素组成分异，因此Mo同位素组成可以示踪地质时期的气候和环境变化、揭示物质迁移规律和成矿作用。在应用MC-ICP-MS分析Mo同位素前，需对样品进行分离纯化，达到富集Mo和去除干扰元素(如Ru)的目的。已有学者开发了地质样品的前处理方法，在现代水圈中的Mo地球化学循环、古环境、古气候和行星演化过程等研究中应用于相关样品的处理。但是传统的阴、阳离子树脂双柱法在处理某些Fe含量特别高且含Ca的特殊地质样品(如含大量黄铁矿的钙质泥岩、钙质页岩)时，需多次过阳离子交换树脂，步骤较繁琐。针对此类特殊地质样品，该文开发了阴离子交换树脂单柱-二次淋洗法，获得Mo回收率>96%，符合质谱仪分析Mo同位素的要求，且Ru的去除率接近100%，比原方法提高了约12%。该方法也适用于处理多种性质的样品，对拓展Mo同位素在地学领域的应用具有重要意义。

92 微波消解-电感耦合等离子体发射光谱法测定粉煤灰中的镓

黄靖，王英滨^*，周冠轩，马真乾

(中国地质大学(北京)数理学院，北京 100083)

镓是一种重要的战略资源，主要从铝土矿中回收获得。随着铝土矿资源的枯竭，需要开发新的途径获取镓。粉煤灰含有丰富的镓元素，准确测定粉煤灰中镓的含量对于实现其回收具有重要作用。粉煤灰的基体复杂，微量镓的浸出存在一定的困难。已报道的地质样品中镓含量的测定方法很多，但存在前处理周期长、过程繁琐、用酸量大、环境污染严重等问题。该文以内蒙古某电厂采集的粉煤灰与粉煤灰标准物质为例，利用硝酸-氢氟酸-盐酸-高氯酸，采用微波消解法处理样品。该方法通过引入盐酸，减少了氢氟酸的用量，因而缩短了除氟时间，在地质样品中微量镓分析领域具有参考价值。

99 固体直接进样-电热蒸发电感耦合等离子体质谱联用分析土壤中的重金属元素

乔磊¹，叶永盛¹，李鹰¹，付永强¹，周建光²，俞晓峰¹

(1.聚光科技(杭州)股份有限公司，浙江杭州 310000;2.浙江大学，浙江杭州 310000)

随着工业化发展，环境重金属污染问题频繁爆发，土壤作为人类赖以生存的重要资源首当其冲。其重金属的准确检测，对于全面、系统地了解土壤环境中重金属的迁移、转化以及提出有效的整治方法具有重要的指导意义。近年来，基于电热蒸发-电感耦合等离子体质谱(ETV-ICP-MS)技术对土壤中重金属含量进行检测成为国内外研究热点。该文通过改进电热蒸发炉结构、优化仪器参数，采用梯度升温、基体匹配校正方法、管路伴热传输和氩气在线稀释等策略，并结合移动车载ICP-MS技术，建立了环境现场固体粉末直接进样ETV-ICP-MS联用定量分析土壤中Cr、Cu、Zn、As、Cd、Hg和Pb等重金属元素的方法。该方法是一种有实用价值的环境现场土壤样品分析技术。

图 1 研究区水系分布及采样点分布

Figure 1. Distribution of water systems and sampling points in the study area.

The red dots in the figure are shallow groundwater sampling points, blue dots are deep sampling points, and the solid blue line is the boundary between shallow water and deep water. According to the spatial structure and distribution of the aquifer and the relative water barrier, the Quaternary water-bearing system is divided into Ⅰ, Ⅱ, Ⅲ and Ⅳ water-bearing groups. As the thickness of the Ⅰ aquifer group is small, most of them are not exploited separately, and the hydraulic connection between the Ⅰ and Ⅱ aquifer groups is close, so it can be regarded as a unified aquifer system, i.e. Ⅰ+Ⅱ aquifer groups, which are "shallow aquifer groups" and are the main exploited layer section for agricultural water. The Ⅲ and Ⅳ aquifer groups are "deep aquifer groups", where the Ⅲ aquifer group is the main mining section for urban life and industrial water in the working area. The direction of groundwater runoff and runoff characteristics of the Ⅰ+Ⅱ aquifer groups and the Ⅲ aquifer group in this area are basically the same, and the direction of groundwater runoff is roughly the same as the topographic tendency and the direction of surface water runoff, i.e. the northern part flows from north west to south east, while the southern part moves from south west to north east.

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图 2 研究区现状地下水化学类型分布图

a—浅层含水层; b—深层含水层。

Figure 2. Distribution of current groundwater chemical types (a. shallow aquifer, b. deep aquifer).

The study area is a single-structure diving area in front of the mountain, with coarse aquifer particles, abundant groundwater recharge, strong alternating circulation, and simple water chemistry type, mainly bicarbonate calcium-magnesium (HCO₃-Ca-Mg) type water with low mineralization. Along the direction of groundwater runoff, the water chemistry type changes from HCO₃-Ca-Mg(Ca) type in piedmont plain, through HCO₃-Mg-Ca, HCO₃-Mg-Ca-Na, HCO₃-Na-Mg-Ca to HCO₃-Cl-Na-Ca, HCO₃-Cl-SO₄-Na to Cl(SO₄)-Na in the central alluvial plain. The distribution of chemical characteristics of deep groundwater is generally controlled by hydrogeological conditions, and is regularly distributed from the piedmont plain to the central plain; compared with shallow groundwater, the chemical type of deep groundwater is relatively simple, from the top of the piedmont plainalluvial floodplain fan to the bottom of the alluvial floodplain fan, and the main anion in most parts of the plain is HCO₃ type; the cations of deep groundwater are relatively complex, and the zonation is more obvious: from the piedmont plain to the bottom of the alluvial floodplain fan, the cations change to HCO₃-Cl-Na and HCO₃-Cl-SO₄-Na. The deep groundwater cations are relatively more complex and more obvious: from the piedmont plain to the bottom of the alluvial fan, the cations transition from Ca, Ca-Mg, Mg-Ca, Na-Mg-Ca (Mg-Ca-Na) type to Na-Ca, Na type water.

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图 3 地下水样品(a, b)吉布斯图; (c)Mg²⁺/Na⁺与Ca²⁺/Na⁺比值关系图; (d)HCO₃^-/Na⁺与Ca²⁺/Na⁺比值关系图

Figure 3. (a, b) Gibbs diagrams of groundwater samples; (c) Ratio relationship chart of Mg²⁺/Na⁺ and Ca²⁺/Na⁺; (d) Ratio relationship charts of HCO₃^-/Na⁺ and Ca²⁺/Na⁺.

Most of the water sample points in the TDS vs. Na⁺/(Na⁺+Ca²⁺) diagram are located in the middle of the diagram, and a few are distributed outside the box, and the points in the TDS vs. Cl^-/(Cl^-+HCO₃^-) diagram are all distributed inside the box. The shallow aquifer groups are basically located within the water-rock interaction area, and individual points show some influence of evaporation concentration. The deep aquifer groups are all subject to water-rock interaction and is less affected by evaporation and atmospheric precipitation. The analysis results show that the milligram equivalent concentration ratio of (Ca²⁺+Mg²⁺)+(HCO₃^-+SO₄^2-) to Na⁺+K⁺-Cl^- is close to-1, indicating that the cation exchange is more significant. Groundwater samples in the study area are mostly distributed near the end elements of silicate minerals, indicating that weathering of silicate minerals is the main hydrogeochemical control factor in the study area.

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图 4 研究区地下水样品主要离子比值图

Figure 4. Major ion ratios of groundwater samples.

Most of the groundwater samples exhibit Cl^-/(Na⁺+K⁺) < 1, indicating that silicate mineral dissolution (such as potassium feldspar and sodium feldspar) is the main source of excess Na⁺ and K⁺, except for rock salt in dissolved state. The HCO₃^-/(Ca²⁺+Mg²⁺) of the shallow aquifer groups samples is basically<1, showing excess Ca²⁺ and Mg²⁺, indicating other sources of Ca²⁺ or Mg²⁺, while the (HCO₃^-+SO₄^2-)/(Ca²⁺+Mg²⁺) of the shallow aquifer groups is distributed above and below the 1∶1 line on both sides, suggesting that evaporite minerals (e.g. gypsum) may also be an important source of Ca²⁺ for the shallow aquifer groups. Both HCO₃^-/(Ca²⁺+Mg²⁺) and (HCO₃^-+SO₄^2-)/(Ca²⁺+Mg²⁺) of the deep aquifer groups are located above the 1∶1 line, with excess HCO₃^- implying silicate dissolution dominance, or the presence of cation exchange, leading to lower Ca²⁺ content. The water samples of the shallow and deep aquifer groups are mainly distributed below the (Cl^-+SO₄^2-)/(HCO₃^-)=1∶1 line, indicating that their chemical components are subject to great dissolution by carbonate rocks

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图 5 地下水样SO₄^2-/Ca²⁺与NO₃^-/Ca²⁺的比值关系图

Figure 5. Relationship between SO₄^2-/Ca²⁺ and NO₃^-/Ca²⁺ in groundwater samples.

The SO₄^2-/Ca²⁺ to NO₃^-/Ca²⁺ ratios of the deep aquifer groups were all greater than 1, except for the 240m water well in the north of Erlangmiao Village, Dingzhou City, Hebei Province, which was less than 1. This indicates that the deep aquifer groups are basically affected by industrial and mining activities, but not by agricultural activities and residential sewage. In the shallow aquifer groups, the SO₄^2-/Ca²⁺ to NO₃^-/Ca²⁺ ratio of 27 water samples is greater than 1, and the SO₄^2-/Ca²⁺ to NO₃^-/Ca²⁺ ratio of 20 water samples is less than 1, which means that the shallow aquifer groups are partly influenced by industrial and mining activities, and partly influenced by agricultural activities and domestic sewage of residents

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表 1 研究区地下水水化学参数统计

Table 1 Statistical results of groundwater hydrochemical parameters in the study area

地下水类型	特征值	pH	TDS (mg/L)	K⁺ (mg/L)	Na⁺ (mg/L)	Ca²⁺ (mg/L)	Mg²⁺ (mg/L)	Cl^- (mg/L)	SO₄^2- (mg/L)	HCO₃^- (mg/L)	NO₃^- (mg/L)
浅层含水层组	最小值	7.35	254.10	0.26	7.61	12.88	14.44	5.26	6.48	177.30	0.20
	最大值	8.92	6015.00	2.69	1393.00	194.00	341.40	693.30	3091.00	558.30	298.40
	平均值	7.90	664.14	1.14	87.49	76.15	47.60	70.66	162.27	333.28	28.78
	标准偏差	0.35	907.40	0.66	218.22	39.03	51.66	120.67	483.46	90.21	48.99
	变异系数	0.04	1.37	0.58	2.49	0.51	1.09	1.71	2.98	0.27	1.70
深层含水层组	最小值	7.40	197.10	0.30	8.26	4.43	1.12	1.75	4.99	155.60	0.71
	最大值	8.80	691.40	2.61	189.80	58.29	20.82	86.22	255.70	305.10	17.46
	平均值	8.03	278.58	1.46	56.52	28.98	10.60	15.37	27.41	221.23	4.55
	标准偏差	0.38	88.95	0.65	37.97	14.91	5.54	19.14	43.89	39.67	4.05
	变异系数	0.05	0.32	0.45	0.67	0.51	0.52	1.25	1.60	0.18	0.89
Note: The test results showed that the largest deviation was in the water sample from Hanbao Village, Liu Lizhuang Town, Anxin County, Baoding City, Hebei Province, which was from the shallow aquifer groups, and the maximum TDS reached 6015.00mg/L. The TDS of the shallow aquifer groups ranged from 254.10 to 6015.00mg/L, with an average of 664.14mg/L, with a large coefficient of variation and a large variation in TDS, indicating that the shallow aquifer groups were affected by meteorological and human factors. The TDS of the deep aquifer group ranged from 197.10 to 691.40mg/L, with an average of 278.58mg/L, and the coefficient of variation was small, indicating that the groundwater of the deep aquifer groups was less affected by meteorological and human activities than that of the shallow aquifer groups. The pH values of the shallow and deep aquifer groups in the study area were not significantly different (7.35-8.92) and were alkaline. The NO₃^-maximum value of 298.40mg/L and the SO₄^2-maximum value of 3091.00mg/L in the shallow aquifer groups, but the average value is not significant, indicating that the shallow aquifer groups have caused local nitrate and sulfate pollution due to agricultural activities and other influences.

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