Reactive transport in unsaturated soil: Comprehensive modelling of the dynamic spatial and temporal mass balance of water and chemical components

By implementing the moisture-based form of Richards’ equation into the geochemical modelling framework PHREEQC, a generic tool for the simulation of one-dimensional flow and solute transport in the vadose zone undergoing complex geochemical reactions was developed. A second-order, cell-centred, explicit finite difference scheme was employed for the numerical solution of the partial differential equations of flow and transport. In this scheme, the charge-balanced soil solution is treated as an assembly of elements, where changes in water and solute contents result from fluxes of elements across cell boundaries. Therefore, water flow is considered in terms of oxygen and hydrogen transport.     

Coupled Reactive Transport Modeling of Redox Processes in a Nitrate-Polluted Sandy Aquifer

The reactive transport modeling of a complicated suite of reactions apparent in the aquifer during the application of N-containing fertilizers is reported. The unconfined sandy aquifer can be subdivided into an oxic zone which contains groundwater with oxygen and nitrate and an anoxic zone characterized by elevated iron and sulfate concentrations in groundwater. Oxygen and nitrate are being reduced by pyrite and organic matter that commonly apparent in the aquifer. The oxidation of pyrite is modeled using the local equilibrium approach, whereas decomposition of organic matter, with the adoption of kinetic approach. The system is buffered by dissolution of aluminum and iron oxides. The modeling process is a two-step procedure. First, the processes are modeled in the one-dimensional (1D) column using PHREEQC code. Subsequently, the calibrated and verified data were copied and used in two-dimensional (2D) PHAST model. Prior to the performance of reactive transport modeling operations with PHAST, a reliable flow model was executed. Finally, predictions are made for the distribution of water chemistry for the year 2008. Model predicts that sulfate derived from the ongoing pyrite oxidation is reduced by the dissolved organic carbon at the higher depth and forms pyrite by the reaction with iron. The results of this study highlight the importance of understanding the interplay between the transport and chemical reactions that occur during the input of nitrate to the aquifer. Reactive transport modeling incorporating the use of a newly developed code PHAST have proved to be a powerful tool for analyzing and quantifying such interactions.     

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。     

内蒙古哈素海区域高砷地下水化学特征及其成因

哈素海区域高砷地下水对当地居民饮用水安全造成严重威胁, 揭示其形成演化机制对科学合理的开发利用水资源、保障居民身体健康具有重要意义。本文在水文地质调查的基础上, 应用Piper三线图、PHREEQC的砷形态计算及相关性分析等方法, 研究高砷地下水化学特征、构建砷形态模型(SM)和砷吸附模型(HSM), 以揭示高砷地下水的成因机制。结果表明, 研究区砷浓度为0.2~231.5 μg/L, 高砷区主要分布在大青山以南的冲湖积平原区; 地下水砷的类型以As(Ⅲ)为主, SM分析显示优势形态为H3AsO3, HSM分析显示存在Hfo_wH2AsO3和H3AsO3两种主要形态。地下水中的砷化物可能来源于山区富砷岩石的风化溶解以及第四系富砷河湖相沉积物; 研究区河湖相沉积环境是高砷水形成的前提, 有机质分解主导的还原环境是导致砷从含水介质释放到地下水中的主要因素, 弱碱性环境和HCO– 3的竞争吸附也会引起砷的释放。     

Mineral Weathering in a Semiarid Mountain River: Its assessment through PHREEQC inverse modeling

By means of PHREEQC inverse modeling, we have simulated the weathering reactions in Los Reartes River, a mountainous (2400–670 m a.s.l.) drainage basin from the Sierras Pampeanas of Córdoba, Argentina, analyzing the effect of lithology, relief, and climate. The steep upper half of the basin (slopes > 20) is occupied by exposed granite; the remaining area is mostly metamorphic, with cropping out gneisses and progressively decreasing slopes (< 6). Climate is semihumid to semiarid; rainfall mainly occurs in summer and decreases with decreasing height. PHREEQC inverse models developed using water chemical data showed that (a) oligoclase was the major supplier of solutes, while the main precipitated phase was kaolinite in the granite domain; (b) muscovite is the chief supplier of solutes and illite is the main precipitated phase in the gneissic realm; (c) the steeper portions of the metamorphic reach are less crucial in supplying solutes than the lower ones, thus highlighting the importance of the water residence time in the kinetics of dissolution; (d) in the driest time of the year (winter, 20 mm/month) we registered the highest production of dissolved and precipitated phases; fluxes (mmol/month), however, are higher at the end of the rainy season; (e) CO₂ consumption is important all along the Los Reartes drainage basin and, in terms of mmol/kg H₂O, the lowermost portion of the basin is the most significant supplier; (f) CO₂ accounts for over 50 of all the species involved in the weathering reactions occurring at the Los Reartes drainage basin.     

Hydrochemistry and source of high fluoride in groundwater of the Nairobi area,Kenya / Hydrochimie et origine des fortes concentrations en fluorure dans l'eau souterraine de la région de Nairobi,au Kenya

Abstract

This study aims to identify the hydrogeochemical processes influencing the high fluoride concentrations in groundwater of the Nairobi area, Kenya. For this purpose 16 groundwater samples were collected and analysed. Fluoride concentrations above the WHO standard are found in the downstream areas. The high F^? concentrations are correlated with high sodium and pH and low Ca²⁺ concentrations. Weathering of sodium-rich alkaline igneous rocks causes a pH increase resulting in an increase in HCO₃ ^? and CO₃ ^2- by dissolution of CO₂. Groundwater becomes oversaturated compared to calcite and calcite precipitation occurs, leading to a decrease in Ca²⁺. This causes a sub-saturation with respect to fluorite and dissolution of fluorite increases the F^? concentration. These reactions were modelled using the PHREEQC model and the results showed a good agreement with the measured groundwater quality, indicating that the proposed reactions are plausible for explaining the observed concentrations in groundwater.     

Reactive-transport modeling of fly ash–water–brines interactions from laboratory-scale column studies

Dynamic leaching tests are important studies that provide more insights into time-dependent leaching mechanisms of any given solid waste. Hydrogeochemical modeling using PHREEQC was applied for column modeling of two ash recipes and brines generated from South African coal utility plants, Sasol and Eskom. The modeling results were part of a larger ash–brine study aimed at acquiring knowledge on (i) quantification and characterization of the products formed when ash is in contact with water–brines in different scenarios, (ii) the mineralogical changes associated with water–brine–ash interactions over time, (iii) species concentration, and (iv) leaching and transport controlling factors. The column modeling was successfully identified and quantified as important reactive mineralogical phases controlling major, minor and trace elements’ release. The pH of the solution was found to be a very important controlling factor in leaching chemistry. The highest mineralogical transformation took place in the first 10 days of ash contact with either water or brines, and within 0.1 m from the column inflow. Many of the major and trace elements Ca, Mg, Na, K, Sr, S(VI), Fe, are leached easily into water systems and their concentration fronts were high at the beginning (within 0.1 m from the column inflow and within the first 10 days) upon contact with the liquid phase. However, their concentration decreased with time until a steady state was reached. Modeling results also revealed that geochemical reactions taking place during ash–water–brine interactions does affect the porosity of the ash, whereas the leaching processes lead to increased porosity. Besides supporting experimental data, modeling results gave predictive insights on leaching of elements which may directly impact on the environment, particularly ground water. These predictions will help develop scenarios and offer potential guide for future sustainable waste management practices as a way of addressing the co-disposal of brines within inland ash dams and heaps.     

伊犁盆地蒙其古尔铀矿床水文地球化学模拟研究

水成铀矿床的形成受控于水文地球化学环境的变化,水-岩体系的pH、Eh值和水化学成分的改变是铀富集成矿的关键因素。笔者根据地质、水文及水化学分析资料,应用PHREEQC软件对伊犁盆地蒙其古尔铀矿床三工河组地下水系统中发生的水文地球化学过程进行模拟,以期确定:1)层间水在径流过程中与含水层发生的化学反应;2)水-岩化学反应发生的条件及进行的程度;3)体系中铀的水文地球化学行为及其成矿的有利条件。     

煤矸石内各矿物组分溶解-释放规律的数值模拟研究

为了更好防治煤矸石山对环境危害,研究了不同温度和CO2分压条件下煤矸石内各矿物的溶解-释放规律。应用美国地质调查所开发的水化学模拟软件PHREEQC对在不同温度和CO2分压条件下煤矸石内各矿物的溶解度进行了水化学模拟。研究结果显示,煤矸石内所有矿物溶解度都随着温度的上升而增大,然而随着溶液中CO2分压的不断增大这种趋势逐渐转变为随着温度的上升溶解度逐渐减小;煤矸石内所有矿物(石英除外)溶解度随着CO2分压的增大而增大。碳酸盐(方解石)的溶解度随着CO2分压升高呈现非线性迅速增大的趋势,其它盐类的溶解度随着CO2分压的升高增大的速率较为缓慢。在煤矸石山内部,某处煤矸石淋溶液内CO2分压越高,其化学组分浸出量也就越大;在矸石山透气性良好时,温度越高煤矸石化学成分的浸出量越大。