Patterns in groundwater chemistry resulting from groundwater flow

 Groundwater flow influences hydrochemical patterns because flow reduces mixing by diffusion, carries the chemical imprints of biological and anthropogenic changes in the recharge area, and leaches the aquifer system. Global patterns are mainly dictated by differences in the flux of meteoric water passing through the subsoil. Within individual hydrosomes (water bodies with a specific origin), the following prograde evolution lines (facies sequence) normally develop in the direction of groundwater flow: from strong to no fluctuations in water quality, from polluted to unpolluted, from acidic to basic, from oxic to anoxic–methanogenic, from no to significant base exchange, and from fresh to brackish. This is demonstrated for fresh coastal-dune groundwater in the Netherlands. In this hydrosome, the leaching of calcium carbonate as much as 15 m and of adsorbed marine cations (Na⁺, K⁺, and Mg²⁺) as much as 2500 m in the flow direction is shown to correspond with about 5000 yr of flushing since the beach barrier with dunes developed. Recharge focus areas in the dunes are evidenced by groundwater displaying a lower prograde quality evolution than the surrounding dune groundwater. Artificially recharged Rhine River water in the dunes provides distinct hydrochemical patterns, which display groundwater flow, mixing, and groundwater ages. Received, May 1998 · Revised, August 1998 · Accepted, October 1998     

Distinguishing groundwater flow paths in different fractured-rock aquifers using groundwater chemistry: Dandenong Ranges, southeast Australia

Major ion geochemistry is used to qualitatively interpret groundwater residence times within an aquifer, and the extent of mixing between aquifers with distinctive mineralogy. In conjunction with hydraulic heads and stable isotope geochemistry, flow paths and inter-aquifer exchange are defined in a fractured-rock aquifer system in the Dandenong Ranges, southeast Australia. Stable isotopes indicate modern seasonal recharge throughout the system. At high elevations in the sub-catchment, which includes both marine Silurian-Devonian sedimentary and Tertiary basalt aquifers, Cl is derived primarily from cyclic salts, and differences in mineralogy result in groundwater from the basalt aquifer having higher TDS contents (123–262 mg/L) and (Ca+Mg)/Na ratios (0.9–1.3) than groundwater from the sedimentary aquifer (TDS: 55–79 mg/L; (Ca+Mg)/Na: 0.1–0.2). At low elevations, in areas of local groundwater discharge, the more regional flow system in the Silurian-Devonian sediments contains additional Cl from water–rock interaction and has distinctly higher TDS contents (517–537 mg/L). Differences in groundwater chemistry between the aquifers and between shallower and deeper flow systems highlights areas of inter-aquifer mixing. This is particularly important for aquifer vulnerability where groundwater quality in the deeper aquifer may be impacted by surface activities.

---

Resumen Se ha utilizado geoquímica de iones mayores para interpretar cualitativamente los tiempos de residencia del agua subterránea dentro de un acuífero, y el grado de mezcla entre acuíferos con mineralogía característica. De manera conjunta con presiones hidráulicas y geoquímica de isótopos estables, se han definido trayectorias de flujo e intercambio entre acuíferos en un sistema de acuífero de roca fracturada en las Sierras Dandenong, sureste de Australia. Los isótopos estables indican recarga estacional moderada a través del sistema. A elevaciones altas en la sub-cuenca que incluye acuíferos sedimentarios Silúrico-Devónicos y acuíferos basálticos Terciarios, Cl se deriva principalmente de sales cíclicas. Las diferencias en mineralogía resultan en agua subterránea del acuífero basáltico que tiene mayores contenidos TDS (123–262 mg/L) y mayor relación (Ca+Mg)/Na (0.9–1.3) que el agua subterránea de los acuíferos sedimentarios (TDS:55–79 mg/L; (Ca+Mg)/Na: 0.1–0.2). A elevaciones bajas, en áreas de recarga local de agua subterránea, el sistema de flujo más regional en los sedimentos Silúrico-Devónicos contiene Cl adicional que se deriva de la interacción roca-agua y típico contenido TDS más alto (517–537 mg L). Las diferencias en la química del agua subterránea entre los acuíferos y entre los sistemas de flujo más profundo y más somero resalta áreas de mezcla entre acuíferos. Esto es particularmente importante para la vulnerabilidad del acuífero donde la calidad del agua subterránea en el acuífero más profundo puede ser impactada por las actividades superficiales.

---

Résumé Les ions majeurs sont utilisés pour interpréter quantitativement les temps de résidence des eaux souterraines dans les aquifères, et létendue des zones de mélange entre les aquifères de différentes minéralogies. En regard de la répartition des charges hydrauliques et des informations données par les isotopes stables, les écoulements et les échanges inter-aquifères sont définis dans un aquifère fracturé dans le Dandenong Ranges, SE de lAustralie. Les isotopes stables indiquent des recharges modernes et saisonnières à travers le système aquifère. A haute altitude dans le sous-bassin versant, qui inclut des sédiments du Siluro-Dévonien et des basaltes du Tertiaire, le chlore est dabord dérivé des sels cycliques, et des différences minéralogiques dans les eaux souterraines sont observées selon laquifère : basalte tertiaire (TDS: 123–262 mg/L; Ca+Mg/Ca: 0.9 à 1.3) et sédiments primaires (TDS: 55–79 mg/L; Ca+Mg/Ca: 0.1–0.2). Aux basses altitudes, dans les zones locales de décharge des eaux souterraines, les écoulements les plus régionaux possèdent des teneurs plus élevées en Chlore en provenance des interactions eau—roche, et des TDS plus élevées (515–537 mg/L). Des différences dans la chimie des eaux souterraines entre les aquifères et entre les systèmes découlement de surface et les écoulements profonds mettent en lumière les zones de mélange inter-aquifère. Ceci est particulièrement important pour la définition de la vulnérabilité où la qualité des eaux souterraines en profondeur peuvent subir les impacts des activités de surface.

     

污水、地下水混合实验分析

将污水与地下水总体积20 L按8∶2、6∶4、4∶6、2∶8混合及分别加砂1 500 g混合;污水20 L与砂1 500 g混合进行污水、地下水混合模拟实验。间隔48 h、96 h、192 h、360 h、600 h取样分析混合后水中各组分浓度,通过混合计算公式计算出各组分浓度和实际测得的各组分浓度进行比较,得到混合水中各组分浓度变化,进而研究污水与地下水及含水介质之间的相互作用和机理。     

A study on the mixing proportion in groundwater samples by using Piper diagram and Phreeqc model

Piper (1944) diagram has been the basis for several important interpretations of the hydrogeochemical data. As seen in this diagram, most natural waters contain relatively few dissolved constituents, with cations (metals or bases) and anions (acid radicles) in chemical equilibrium with one another. Apart from the facies representation, the composition of the mixed sample can be identified in terms of the composition of the parental solution. To bring out this advantage of the Piper diagram, a study was conducted in the Kalpakkam region of Tamilnadu, South India. By taking the geology and water table into consideration, two sample locations were selected as parent solution and third one as the mixture sample. All three samples were analyzed for calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), chloride (Cl), sulphate (SO4) and phosphate (PO4) by Ion Chromatograph (Metrohm IC 861). HCO3 was determined by volumetric titration. The Piper diagram shows that parent solutions clustered towards Na-Mg-Ca-HCO3-Cl and Na-HCO3 facies, and the mixing sample belongs to Na-Mg-HCO3 facies. Phreeqc interac-tive (Ver 2.8) along with the original composition of the mixture sample was used to correlate the mixing proportion identified by the Piper diagram.     

Temporal interpolation of groundwater level hydrographs for regional drought analysis using mixed models

Large-scale studies of the spatial and temporal variation of groundwater drought status require complete inventories of groundwater levels on regular time steps from many sites so that a standardised drought index can be calculated for each site. However, groundwater levels are often measured sporadically, and inventories include missing or erroneous data. A flexible and efficient modelling framework is developed to fill gaps and regularise data in such inventories. It uses linear mixed models to account for seasonal variation, long-term trends and responses to precipitation and temperature over different temporal scales. The only data required to estimate the models are the groundwater level measurements and freely available gridded weather products. The contribution of each of the four types of trends at a site can be determined and thus the causes of temporal variation of groundwater levels can be interpreted. Validation reveals that the models explain a substantial proportion of groundwater level variation and that the uncertainty of the predictions is accurately quantified. The computation for each site takes less than 130 s and requires little supervision. Hence, the approach is suitable to be upscaled to represent the variation of groundwater levels in large datasets consisting of thousands of boreholes.

     

Simulation of groundwater flow and contaminant transport at a landfill site using models

Numerical and analytical modelling studies were conducted for the analysis of groundwater flow and contaminant transport at the Innisfil landfill site in the Town of Innisfil, County of Simcoe, in Ontario, Canada. Previously conducted field studies categorized the upper stratigraphy at the site into three units: upper sand unit, upper silt/clay unit and Intermediate Sand unit. Essentially horizontal groundwater movement in the two sand units and vertical downward flow in the silt/clay unit were reported by the field hydrogeologists. In the following, application of three computer models (FLOWPATH, USGS MOC and POLLUTE) for the simulation of the groundwater flow and contaminant transport processes at the Innisfil landfill site is described. The paper focuses on the calibration of groundwater flow and contaminant transport systems, and demonstrates how the insight gained during the contaminant transport calibration was used to improve the initial groundwater flow characterization of the hydrogeological system.     

Statistical models for the assessment of nitrate contamination in urban groundwater using GIS

The purpose of this study is to develop statistical models for groundwater quality assessment in urban areas using Geographic Information Systems (GIS). To develop the models, the concentrations of nitrate (expressed as nitrogen, NO₃-N), which are different according to the type of land use, well depth and distribution of rainfall, were analyzed in the Seoul (the capital of South Korea) area. Data such as land use, location of wells and groundwater quality data for nitrate contamination were collected and a database constructed within GIS. The distribution of NO₃-N concentrations is not normal, and the results of the Mann-Whitney U-test analysis show the difference of NO₃-N concentration by well depth and by distribution of rainfall. In both the shallow and deep wells, the radius of influence is 200 m in the dry season and 250 m in the rainy season, showing the tendency to increase in the rainy season. The results of correlation and regression analysis indicate that mixed residential and business areas and cropped field areas are likely to be the major contributor of increasing NO₃-N concentration. Land uses are better correlated with NO₃-N in deep wells than in shallow wells.     

地下水管理模型研究进展

本文在分析和总结前人研究成果的基础上,将地下水管理模型的研究过程划分为两大阶段:模型理论探索到推广应用阶段(1970~1990年)和模型实用性研究阶段(1990年至今)。在对各阶段的研究内容以及存在问题等进行概述的基础上,指出建立地下水资源管理的多目标动态规划模型将是未来地下水管理模型的发展方向和趋势,但需要采用更为先进的优化算法对其进行求解,同时对地下水管理模型与GIS技术的集成进行了展望。     

Shallow groundwater and soil chemistry response to 3 years of subsurface drip irrigation using coalbed-methane-produced water

Disposal of produced waters, pumped to the surface as part of coalbed methane (CBM) development, is a significant environmental issue in the Wyoming portion of the Powder River Basin, USA. High sodium adsorption ratios (SAR) of the waters could degrade agricultural land, especially if directly applied to the soil surface. One method of disposing of CBM water, while deriving beneficial use, is subsurface drip irrigation (SDI), where acidified CBM waters are applied to alfalfa fields year-round via tubing buried 0.92 m deep. Effects of the method were studied on an alluvial terrace with a relatively shallow depth to water table (～3 m). Excess irrigation water caused the water table to rise, even temporarily reaching the depth of drip tubing. The rise corresponded to increased salinity in some monitoring wells. Three factors appeared to drive increased groundwater salinity: (1) CBM solutes, concentrated by evapotranspiration; (2) gypsum dissolution, apparently enhanced by cation exchange; and (3) dissolution of native Na–Mg–SO₄ salts more soluble than gypsum. Irrigation with high SAR (～24) water has increased soil saturated paste SAR up to 15 near the drip tubing. Importantly though, little change in SAR has occurred at the surface.     

Understanding groundwater sources and movement using water chemistry and tracers in a low matrix permeability terrain: the Cretaceous (Chalk) Ulster White Limestone Formation,Northern Ireland

The Cretaceous Chalk [Ulster White Limestone Formation (UWLF)] in Northern Ireland has been diagenetically altered to a hard, low porosity, low matrix-permeability rock. It subcrops extensive beneath thick horizontal Tertiary Basalt lavas, but has a restricted strip of outcrop (approximately 80 km²) around the periphery of the overlying igneous rock. Despite its nature and location, numerous springs issue from the Chalk and are used for public and local supply, although little is known about the origin of the groundwater or the type of flow within the Chalk. We have addressed these unknowns using hydrogeochemical data from both rock types and surface stream waters, and fluorescent dye tracing. We have demonstrated that leakage recharge from the basalt to the Chalk accounts for less than 20% of the total water issuing from the Chalk springs using geochemical mass balance of conservative species and discharge data. The majority of the discharge derives from streams coming off the basalt and entering sink holes in the Chalk aquifer. Field and water tracing evidence shows that groundwater flow in the Chalk is dominated by conduit and fissure flow near to the outcrop areas. Karstification has been widespread near outcrop but has not ocurred in the sub-basalt region. Beneath the basalts, the Chalk exhibits different hydraulic properties due to the reduced recharge and dissolution potential that has prevented extensive development of fissure permeability in the UWLF. The Chalk aquifer thus appears to be strongly zoned in terms of the source of water, flow regime and recharge rate.     

Resolving archaeological populations with Sr-isotope mixing models

Strontium isotope analysis of tooth enamel is a useful provenancing technique to investigate the childhood origins and residential mobility of ancient people. However, where different geographical target regions have similar biosphere ⁸⁷Sr/⁸⁶Sr it is often difficult to resolve the ⁸⁷Sr/⁸⁶Sr ranges of two different groups of people and establish what constitutes the local range at each site. Here a multi-period study is presented from the Outer Hebrides, Scotland and an investigation of Neolithic and Early Bronze Age populations from the Yorkshire Wolds, NE England. The aim is to demonstrate that, despite complex human dietary strategies, simple mixing systems with only two end-members do occur in archaeological human populations in certain geological provinces and, despite overlapping ⁸⁷Sr/⁸⁶Sr ranges, it is possible to separate two populations based on the structure within the data set.     

Recharge and groundwater models: an overview

Recharge is a fundamental component of groundwater systems, and in groundwater-modeling exercises recharge is either measured and specified or estimated during model calibration. The most appropriate way to represent recharge in a groundwater model depends upon both physical factors and study objectives. Where the water table is close to the land surface, as in humid climates or regions with low topographic relief, a constant-head boundary condition is used. Conversely, where the water table is relatively deep, as in drier climates or regions with high relief, a specified-flux boundary condition is used. In most modeling applications, mixed-type conditions are more effective, or a combination of the different types can be used. The relative distribution of recharge can be estimated from water-level data only, but flux observations must be incorporated in order to estimate rates of recharge. Flux measurements are based on either Darcian velocities (e.g., stream baseflow) or seepage velocities (e.g., groundwater age). In order to estimate the effective porosity independently, both types of flux measurements must be available. Recharge is often estimated more efficiently when automated inverse techniques are used. Other important applications are the delineation of areas contributing recharge to wells and the estimation of paleorecharge rates using carbon-14. Electronic Publication     

Variogram models for regional groundwater geochemical data

Four variogram models for regional groundwater geochemical data are presented. These models were developed from an empirical study of the sample variograms for more than 10 elements in groundwaters from two geologic regions in the Plainview quandrangle, Texas. A procedure is given for the estimation of the variogram in the isotropic and anisotropic case. The variograms were found useful for quantifying the differences in spatial variability for elements within a geologic unit and for elements in different geologic units. Additionally, the variogram analysis enables assessment of the assumption of statistical independence of regional samples which is commonly used in many statistical procedures. The estimated variograms are used in computation of kriged estimates for the Plainview quadrangle data. The results indicate that an inverse distance weighting model was superior for prediction than simple kriging with the particular variograms used.     

数值模型在地下水管理中的应用

为进一步推动模拟工作，并使模拟尽可能标准化和规范化，介绍国际上认可的建立模型的步骤、方法以及常用的模拟软件。引用作者在国外所做的两个实例，对建立模型的步骤、方法以及模型标定方法和标定结果作了具体的介绍。国内应鼓励使用已有的国际标准化模拟软件，进一步提高建模的专门知识和技巧。数值模型是真实世界的一个数学表达，对模型的产出应有一个现实的看法和专业的理解。模型建立前，应对现场数据作详细的专业分析，以确保概念模型的正确。在模型的建设中，应把注意力放在如何使模型在水文地质和物理过程方面去逼近真实世界。模型中采用的计算条件或方法都应有水文地质依据作支持，而不能仅仅为了逼近实测数据而随意地加入无依据的计算条件，这样的模型是不可靠的，其结果将是无实际意义的或是误导的。     

Evaluation of alternative conceptual models for groundwater modelling

This study evaluates the alternative conceptual models for groundwater modelling. A true model was created with a synthetic alluvial fan-plain hydrogeological framework. Various alternative conceptual models were evaluated for groundwater flow simulations. The first alternative model is a single aquifer layer model; the second alternative model is a 3-layer aquifer model; and the third model is a 5-layer model consisting of 3 aquifers separated by 2 aquitards. All models could fit very well to the observations with optimized values of hydraulic conductivities. However, the single aquifer layer model can only compute water balance components with good accuracy. The 3-layer aquifer model can be used for water balance computation and groundwater head simulation with small errors. The 5-layer model is capable of simulating water budget, groundwater head distribution and travel times with high accuracy. Multi-model analysis found only the 3rd alternative model superior.