Inverse geochemical modeling of groundwater salinization in Azraq Basin,Jordan

The aim is to define the mechanism of chemical reactions that are responsible for the salinization of the Azraq basin along groundwater flow path, using inverse modeling technique by PHREEQC Interactive 2.8 for Windows. The chemical analysis of representative groundwater samples was used to predict the causes of salinization of groundwater. In addition, the saturation indices analysis was used to characterize the geochemical processes that led to the dissolution of mineral constituents within the groundwater aquifer system. According to the modeling results, it was noted that the groundwater at the recharge area was undersaturated with respect to calcite, dolomite, gypsum, anhydrite, and halite. Thus, the water dissolved these minerals during water rock interaction, and therefore, the concentration of Ca, Mg, Na, and SO₄ increased along the groundwater flow path. Furthermore, the groundwater at the discharge area was oversaturated with respect to calcite and dolomite. This meant that the water would precipitate these minerals along the flow path, while the water was undersaturated with respect to gypsum and halite throughout the simulated path; this showed the dissolution processes that take place during water-rock interaction. Therefore, the salinity of the groundwater increased significantly along the groundwater flow paths.     

峰峰矿区东部地下水水文地球化学模拟

应用离子比例系数法分析了峰峰矿区东部地下水化学成分特征,结合含水层岩性条件,为水文地球化学模拟中“可能矿物相”的确定提供依据;采用PHREEQC软件对含水层中水-岩作用进行水文地球化学模拟,模拟计算出饱和指数,通过质量平衡模拟计算水-岩作用过程中主要矿物相的转化量。结果表明:方解石和白云石处于饱和状态,在适当的条件下会沉淀,而岩盐、石膏处于未饱和的状态,在适当的条件下将继续溶解。沿地下水流路径,从五矿奥灰水-一矿奥灰水-一矿副井水,地下水系统中白云石、岩盐、石膏溶解,方解石沉淀,且发生了阳离子交换作用。研究矿井水中水-岩相互作用,初步探讨废弃矿井水文地球化学演化机制,对分析矿井水文地球化学演化的影响因素有重要作用。      

咸阳城区地下热水地球化学演化模拟

应用水文地球化学模拟(PHREEQC软件)对咸阳城区地下热水进行了水文地球化学演化和路径模拟.模拟路径分别为西、西北两个补给方向.模拟结果表明,,地下水流向发生了一系列的水-岩反应,,线R5→SP2,SP2水化学类型由Na-HCO2-Cl转化为Na-Cl型,而西北线R6→SP2水化学类型由Na-Ca-HCO3 -el转化为Na-Cl型,在水流路径上SiO2(玉髓)、方解石、白云石和高岭石发生了沉淀,而岩盐、石膏、天青石、钠长石、云母和萤石发生了溶解作用.对研究区地下热水地球化学反应路径模拟,描述了研究区地下热水补给到排泄的演化特征,表明水-岩作用模拟对于揭示研究区地下水化学演化环境具有重要的指示意义.     

人工补给对含水层水质的影响

为了研究人工补给对含水层水质的影响问题,通过反向地球化学模拟方法对大庆西部地下水水质演化规律进行了分析。结果表明,地下水化学成分主要受含水层矿物相的溶解-沉淀作用、阳离子交换吸附作用以及氧化还原作用的影响,并确定方解石、白云石、盐岩、萤石、石膏、赤铁矿、菱铁矿、软锰矿、二氧化碳、阳离子交换剂等为影响地下水化学成分的控制性（矿）物相。在此基础上,采用正向地球化学模拟方法,以大庆市西水源地下水人工补给为例,模拟了地表水进入到地下后与含水层中原有的地下水以及含水层介质发生的水-岩相互作用。模拟结果表明,注入水与含水层中的水混合后,使地下水的矿化度有所降低,且混合水中地表水所占比例越大,地下水的矿化度越低;注入水与含水层中的地下水混合后,不会导致地下水水质的突变和水质级别的降低,还可在一定程度上改善含水层水质。     

Groundwater geochemistry of Ain Azel area,Algeria

Hydrogeochemical data for 18 groundwater samples and 11 hydrochemical parameters were subjected to Q- and R-mode cluster analysis and inverse geochemical modeling. Q-mode cluster analysis resulted in three distinct water types (brackish water type, saline water type and highly saline water type). R-mode cluster analysis led to the conclusion that the water–rock interaction is the major source of contamination for the groundwater in the area. Geochemical modeling results show that carbonates, gypsum, halite, carbon dioxide (gas), and chlorite are dissolving, whereas Ca-montmorillonite, gibbsite, illite, K-mica, kaolinite, and quartz are mostly precipitating along different flow paths in the groundwater system of the area.     

基于反向地球化学模拟的地下水形成作用: 以安徽省泗县为例

在了解安徽省泗县水文地质条件基础上,分析了区域水文地球化学特征及类型,探讨了其空间分布特征。根据开采条件下的地下水动力场条件,选择了3条模拟路径,采用PHREEQC软件进行了水文地球化学模拟研究,定量分析了地下水的形成机理及演化。结果表明,路径Ⅰ发生了岩盐、石膏以及伊利石的溶解,高岭土、石英、白云石、萤石发生了沉淀;钙蒙脱石、方解石不参与反应,NaX解吸,CaX_2被吸附;路径Ⅱ发生了岩盐、石膏、伊利石、石英等的溶解以及钙蒙脱石、方解石的沉淀,NaX解吸,CaX_2被吸附;路径Ⅲ发生的反应基本与路径Ⅰ相同,不同之处在该路径上的白云石发生了溶解,其原因可能是地下水在径流过程中溶解CO_2,使其继续溶解白云石以及受沉淀滞后的影响。研究结果表明地下水开采条件下,泗县地下水化学组分主要受到了岩盐和石膏等矿物的溶解作用、钙钠离子交换作用以及钙蒙脱石、方解石沉淀作用的控制。     

高放废物处置库甘肃北山野马泉预选区地下水化学特征及水-岩作用模拟

在高放废物处置库场地选择和性能评价中,地下水化学特征是最重要的因素之一。文中以野外水文地球化学调查资料为基础,应用水文地球综合分析方法和地下水地球化学模拟技术,探讨中国高放废物处置库甘肃北山野马泉预选区地下水化学特征、时空分布规律及水岩作用机理。主要结论是:野马泉地区地下水以咸水为主, 具有高矿化的特征,水化学类型以Cl·SO4 Na和SO4·Cl Na型为主,pH值大多在7~8 之间;地下水化学成分显示出明显的分带特征;地下水对石盐和石膏欠饱和,对黄铁矿以及铝硅酸盐过饱和;方解石、钠长石在补给区地下水中呈不饱和状态,在排泄区地下水中呈饱和状态。由水岩作用模拟可知,沿水流路径地下水溶解岩石中的钠长石、黑云母、石盐等矿物,溶解二氧化碳,沉淀析出方解石、伊利石和萤石等矿物;发生明显地下水蒸发作用、二氧化碳溶解作用和Ca2+/ Na+离子交换作用, 说明溶滤、沉淀、离子交换和蒸发浓缩作用是区内地下水化学行为的控制因素。     

小昌马河流域地表水地下水同位素与水化学特征及转化关系

利用小昌马河流域上游大雪山老虎沟冰雪融水及下游昌马洪积扇区地下水的稳定同位素和水化学资料, 对流域稳定同位素和水化学的组分特征和季节变化进行了分析. 结果表明: 小昌马河流域内从上游冰雪融水区到下游昌马洪积扇地下水排泄区矿化度不断增高, 水化学类型由HCO₃-Mg-Ca过渡到HCO₃-SO₄-Ca-Mg; 上游冰雪融水与下游地下水δ¹⁸O的季节变化基本一致, 洪积扇区地下水来源于冰雪融水的补给. 水文地球化学模型模拟显示地下水形成过程中水岩作用以析出方解石, 吸收二氧化碳, 溶解石膏、 岩盐和绿泥石等为主要特征, 溶蚀的含盐矿物使地下水中氯化物、 硫酸根和钠离子含量升高, 地下水水质恶化. 同位素和水化学证据均揭示了小昌马河流域地表水-地下水的化学环境转化关系.     

银川平原深层地下水14C年龄校正

地下水¹⁴C年龄的校正精度取决于对地下水溶解无机碳演化过程中影响地下水¹⁴C活度主要因素的准确识别及其影响程度的定量评价。以银川平原为例,在进行银川平原承压水反向地球化学反应路径模拟的基础上,识别出影响区内深层地下水碳酸演化的主要作用并进行深层地下水¹⁴C年龄的校正。研究认为,控制银川平原深层地下水化学演化的主要反应路径为碳酸盐矿物的沉淀和长石、角闪石、石膏等矿物的溶解以及Ca-Na离子交换。地下水流路径上所发生的水文地球化学反应对路径上¹⁴C的浓度变化影响较小。地下水¹⁴C年龄校正结果表明,除补给区和承压水水位漏斗区外,银川平原承压水年龄均在2 000 a以上,属“古水”,天然条件下径流缓慢、地下水更新速度小。在承压水水位漏斗区外,沿地下水流方向,地下水年龄逐渐增大;而在承压水集中开采区,承压水的年龄明显小于路径上游地下水,潜水与承压水之间的垂向水力联系比较密切。     

The origin of fluoride in the granitic aquifer of Porto Alegre, Southern Brazil

The Porto Alegre region, Southern Brazil, comprises a fractured aquifer system constituted by pre-Cambrian granitic and gneissic rocks, and a porous aquifer system formed by Cenozoic muddy–sandy to sandy sediments. A model is presented for the origin of the fluoride in the groundwater of the fractured aquifer system, based on ionic interrelations, a statistical analysis of physicochemical parameters and geochemical modeling. The fluoride is present at levels of up to 6.13 mg/L in groundwater and it arises due to the dissolution of secondary fluorite filling fractures in the granitic and gneissic rocks. The dissolution of fluorite occurs at the same time as calcite and dolomite solubilization. The statistical analysis identified three chemically distinct groups (named 1, 2 and 3) and two subgroups (1A and 1B) of groundwater in the fractured aquifer. The most significant differences between these groups are the different concentration ranges of fluoride, calcium, bicarbonate, magnesium, total dissolved solids and chloride and pH values, as well as the correlations between them. The compositional evolution of each groundwater group is governed mainly by how much high-salinity groundwater from the porous aquifer system is mixed with them and the different thermodynamic equilibrium conditions of calcite, dolomite and fluorite.     

河北平原深层碱性淡水形成的水文地球化学模拟——以保定、沧州地区为例

以揭示河北平原深层碱性淡水化学形成机制为主要研究目的, 选择河北平原深层碱性淡水发育的保定、沧州地区为典型研究区, 应用水文地球综合分析方法和地下水地球化学模拟技术, 探讨了深层碱性淡水水化学性质、分布规律及形成的自然环境; 依据质量守恒原理建立深层地下水质量平衡反应模型, 研究了从山前至滨海整个水流路径上所发生的水文地球化学作用及水、岩间的质量交换, 从而揭示了深层地下水化学演化规律的内涵及深层碱性淡水水化学形成机制.主要结论是深碱性淡水是由山前补给区HCO₃-Ca·Mg水逐步演化而来, 从山前至中部平原, 在地下水环境由开放转为封闭的过程中, 方解石、白云石溶解和沉淀, 钠长石、石膏、岩盐和菱铁矿的溶解, Ca-Na阳离子交换是控制其形成和演化的主要水文地球化学作用.      

Hydrogeochemical evaluation of fractured Limestone aquifer by applying a geochemical model in eastern Nile Valley,Egypt

Rock water interactions play an important role in the flow of groundwater. Groundwater samples were collected from deep production wells with depths ranging from 120 to 230 m. Complete chemical analysis of 40 groundwater samples was collected from the fractured limestone aquifer including major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and major anions (Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?). A geochemical modeling (NETPATH Software) was applied for environmental simulate net geochemical mass-balance reactions between initial and final waters along a hydrologic flow path. This program simulates selected evolutionary waters for every possible combination of the plausible phases that account for the composition of a selected set of chemical constraints in the system. The groundwater of the Eocene aquifer mainly belongs to fairly fresh water with salinity contents ranging from 228 to 3595 ppm. The measured groundwater levels range between 8 and 25 m near the river Nile to the limestone plateau (eastwards). Consequently, groundwater flows from east to westward toward the river Nile. Groundwater aquifer in the study area is mainly composed of fractured limestone; the saturated states of the PCO₂, calcite, aragonite, dolomite, siderite, gypsum, anhydrite, hematite, and goethite in addition to H₂ gas were estimated. The undersaturated state of carbon dioxide reflects closed conditions and very low probability of recent recharge, and it reveals also the high tendency of water to precipitates carbonate species. Undersaturation by carbonate minerals is only restricted to some pockets distributed on the different places of the aquifer in the study area. The majority of groundwater samples of Eocene aquifer in the study area indicated that groundwater is not suitable for irrigation with treatment and requires good drainage.     

鄱阳湖流域赣江下游水化学特征及人类健康风险评价

人类活动对鄱阳湖赣江流域水质的影响受到广泛关注,厘清流域内污染水体对人类的健康风险状况有利于更好地保护和利用水资源。本研究于赣江下游采集39个地下水和16个地表水样,在分析其水化学特征和影响因素的基础上,对地下水水化学成分演变进行反向模拟,并对地下水水质以及潜在非致癌风险进行评价。结果表明,研究区地下水呈弱酸性-中性(pH=5.47~7.60),以HCO₃-Ca-Mg型水为主,部分为Cl-Ca-Mg型水,硅酸岩风化和矿物溶解-沉淀作用是水化学类型形成的主要控制因素;地表水呈中性-弱碱性(pH=6.94~8.19),主要为HCO₃-Cl-Ca-Na型水,其形成与硅酸岩风化、大气降水和人类活动有关。PHREEQC模拟计算结果表明,地下水中大部分矿物饱和指数(SI)为负数,其中岩盐的SI为-7.80~-9.53,指示该矿物溶解剧烈;白云石、石膏和方解石的SI分别为-1.72~-6.39、-1.65~-3.96、-0.51~-3.09,表明三种矿物呈溶解趋势。反向模拟结果显示,赣江干流地下水化学特征演变过程经历了Ca-蒙脱石、岩盐、白云石溶解和方解石沉淀,同时消耗CO₂;支流中命名为NCGW-3的路径表现为高岭石、方解石、玉髓和白云石溶解,石膏、Ca-蒙脱石、黑云母和斜长石沉淀,同时产生CO₂,可能与人为作用的干扰有关。其余支流地下水反向模拟结果与干流结果相似。熵权水质指数(EWQI)计算结果表明,干流地下水水质优于支流地下水,沿赣江受Mn、N {\mathrm{O}}_3^{-}影响水质降低;地下水非致癌潜在风险主要为对婴儿存在严重风险,其次是儿童,对成年男性和成年女性风险相对较小,支流水质存在的潜在风险相较于干流更为显著。     

Regional groundwater flow and geochemical evolution in the Amacuzac River Basin,Mexico

An approach is presented to investigate the regional evolution of groundwater in the basin of the Amacuzac River in Central Mexico. The approach is based on groundwater flow cross-sectional modeling in combination with major ion chemistry and geochemical modeling, complemented with principal component and cluster analyses. The hydrogeologic units composing the basin, which combine aquifers and aquitards both in granular, fractured and karstic rocks, were represented in sections parallel to the regional groundwater flow. Steady-state cross-section numerical simulations aided in the conceptualization of the groundwater flow system through the basin and permitted estimation of bulk hydraulic conductivity values, recharge rates and residence times. Forty-five water locations (springs, groundwater wells and rivers) were sampled throughout the basin for chemical analysis of major ions. The modeled gravity-driven groundwater flow system satisfactorily reproduced field observations, whereas the main geochemical processes of groundwater in the basin are associated to the order and reactions in which the igneous and sedimentary rocks are encountered along the groundwater flow. Recharge water in the volcanic and volcano-sedimentary aquifers increases the concentration of HCO₃ ^–, Mg²⁺ and Ca²⁺ from dissolution of plagioclase and olivine. Deeper groundwater flow encounters carbonate rocks, under closed CO₂ conditions, and dissolves calcite and dolomite. When groundwater encounters gypsum lenses in the shallow Balsas Group or the deeper Huitzuco anhydrite, gypsum dissolution produces proportional increased concentration of Ca²⁺ and SO₄ ^2–; two samples reflected the influence of hydrothermal fluids and probably halite dissolution. These geochemical trends are consistent with the principal component and cluster analyses.     

天津市宁河北奥陶系灰岩水源地的水文地球化学模拟

天津市宁河北水源地属埋藏型地下水源地,其开采层奥陶系灰岩含水层呈北东向的向斜展布,隐伏于石炭系-二叠系砂页岩之下,并被新近系覆盖,仅在东北部与第四系含水层有水力联系,地下水的补给主要来自浅层第四系含水层的越流补给。应用水文地球化学模拟方法,研究从第四系含水层到奥陶系含水层地下水经历的水-岩作用,包括方解石、白云石、萤石和硬石膏的溶解或沉淀、二氧化碳气体的溶解或逸出等,地下水硬度、矿化度总体上有下降趋势,这是由于含Ca²⁺、Mg²⁺和HCO^-₃的矿物相发生溶解,迁入溶液的比率要小于发生沉淀迁出溶液的比率,具体表现在从第四系含水层到奥陶系含水层Ca²⁺、和HCO^-₃浓度的降低幅度较大。通过模拟计算,可以定量确定从补给区到研究区沿水流路径上的水-岩相互作用及质量交换,有助于揭示该区地下水化学环境的演化机制。     

反向地球化学模拟技术在地下水14C年龄校正中应用的进展与思考

地下水¹⁴C年龄校正一直是地下水年代学研究中的一个热点问题,将反向地球化学路径模型与同位素质量传输模型耦合起来,在综合考虑不同碳源、不同水文地球化学反应对¹⁴C质量传输影响的基础上,提出了一种新的综合性的校正方法,从而使地下水¹⁴C定年技术得到了进一步发展。识别深层地下水演化过程中影响¹⁴C浓度变化的主要因素并定量确定其对地下水¹⁴C浓度的影响程度是地下水¹⁴C校正的精度和可信度的重要考虑因素;在应用水文地球化学路径模拟技术进行地下水¹⁴C年龄校正时,必须要充分考虑地下水补给环境特点以及反向地球化学模拟模型中的非可行解的排除。     

Chemical evolution of groundwater in the River Danube deposits in the southern part of the Pannonian Basin (Hungary)

Processes controlling the groundwater chemical composition were studied in the River Danube deposits, in the southeastern part of Hungary. PHREEQM, a combined geochemical and one-dimensional transport model and PHREEQE, NETPATH and WATEQF geochemical computer codes were used to simulate these processes. The main processes controlling water chemistry are equilibrium with calcite, undersaturation in dolomite and albite weathering in the recharge area, ion exchange along the flow path, and ion exchange and mixing with old water at the end of the flow path. Ion exchange seems to be the most important process controlling groundwater chemistry along the flowpath in the fluvial sediments studied. Isotopic data support the geochemical model. The groundwater ages, adjusted for the modeled C mass transfer range from 3300 to 20 200 a B.P. Cation exchange suggests that displacement of a former aqueous solution by the present groundwater occurred. This displacement is attributed to tectonic and paleoclimatic events at the end of the Pleistocene.     

地下水矿物饱和度的水文地球化学模拟分析--以娘子关泉域岩溶水为例

通过分析娘子关泉域岩溶水的水文地质条件、岩溶发育规律以及水文地球化学特征，发现在该泉域内不应出现方解石、白云石、石膏等矿物溶解饱和状态。运用地球化学模拟软件PHREEQC模拟该区可能的化学条件（地下水中二氧化碳分压）及相应条件下的矿物溶解状态，同时结合野外溶解实验推断所处条件范围。这一研究推测出地下水与其溶解矿物所处极限状态应为饱和状态，而实际常常应处于非饱和状态，若计算为过饱和状态，则应可能是分析数据错误所致。     

Identification of the origin of salinization in groundwater using multivariate statistical analysis and geochemical modeling: a case study of Kaohsiung,Southwest Taiwan

The study of brine aquifers in southern Taiwan is highly complicated by hybrid geochemical reactions, which obscure important geochemical information. Using multivariate analysis on major and minor ion compositions normalized by Cl⁻ content, chemical constituents were combined into two principal components representing brine mixing and mineral precipitation. Comparing to multivariate analysis on the original data, this procedure reveals more geochemical information. It demonstrates that the brine groundwater of the region is primarily composed of highly evaporated seawater. The evaporation ratio is >70%; a point at which calcite, dolomite and gypsum precipitate. Oxygen and hydrogen isotopic compositions confirm this inference; and further, geochemical modeling quantitatively determined the evaporation ratio to be about 85%. Natural boron contamination is a consequence of brine groundwater. Two evolutionary trends in the plotting of the Cl/B ratio versus Cl⁻ can be identified: (1) Cl/B ratio decreases with boron being released from clay minerals when brine aquifers are flushed with freshwater; and (2) Cl/B ratio increases when seawater of a high Cl/B ratio infiltrates coastal aquifers.     

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO₂ initially, and open to organic carbon at more distant points down gradient.