Groundwater geochemistry in shallow aquifers above longwall mines in Illinois, USA

 Aquifers above high-extraction underground coal mines are not affected by mine drainage, but they may still exhibit changes in groundwater chemistry due to alterations in groundwater flow induced by mine subsidence. At two active longwall mine sites in Illinois, USA, glacial-drift aquifers were largely unaffected by mining, but the geochemistry of the bedrock aquifers changed during the post-mining water-level recovery. At the Jefferson site, brackish, high-sulfate water present in the upper bedrock shale briefly had lower values of total dissolved solids (TDS) after mining due to increased recharge from the overlying drift, whereas TDS and sulfate increased in the sodium-bicarbonate water present in the underlying sandstone due to downward leakage from the shale and lateral inflow of water through the sandstone. At the Saline site, sandstones contained water ranging from brackish sodium-chloride to fresh sodium-bicarbonate type. Post-mining recovery of the potentiometric levels was minimal, and the water had minor quality changes. Longwall mining affects geochemistry due to subsidence-related fracturing, which increases downward leakage from overlying units, and due to the temporary potentiometric depression and subsequent recovery, whereby water from surrounding areas of the aquifer recharges the affected zone above and adjacent to the mine. Received, December 1998 / Revised, August 1999 / Accepted, August 1999     

Nitrate pollution of ground waters from shallow basaltic aquifers,Deccan Trap Hydrologic Province,India

Analyses of groundwater samples collected from several locations in a small watershed of the Deccan Trap Hydrologic Province, indicated anomalously higher values of nitrate than the background. However, the NO₃ concentrations in water from dug wells under pastureland where the subsurface material consisted of stony waste were minimum. The maximum values were reported for water from dug wells where the principal land use was agricultural. Lowering of NO₃ values under shallow water-table conditions suggests denitrification. Higher concentrations of nitrate determined for samples collected from the wells with a deeper water-table indicate that denitrification process is inactive. The high values of nitrate coinciding with agricultural land use indicate fertilizers as the main source of nitrate pollution of ground-water. Decrease in Cl/NO₃ ratio for agricultural land use confirms this inference.     

Application of geochemistry and radioactivity in the hydrogeological investigation of carbonate aquifers (Sierras Blanca and Mijas,southern Spain)

The chemical characteristics, ³H contents and radioactivity of groundwaters from the Sierras Blanca and Mijas (Southern Spain) have been studied in relation to the chemical composition and radioactivity of the aquifer host rocks, and the residence time of the water. The Sierras Blanca and Mijas are made up of calcitic and dolomitic marbles of Triassic age. The groundwaters that drain the calcitic marbles (which outcrop principally in the western Sierra Blanca) have less mineralization, which descreases quickly with recharge (as does the ³H content), and the gross alpha and beta activities are below detection limit. This is due to the short residence time of water inside the aquifers which are conduit flow systems. The waters of the dolomitic marbles (eastern Sierra Blanca and Sierra Mijas) have higher and less variable mineralization and contain greater concentrations of Mg²⁺, SiO₂ and SO²⁻₄ (ions normally associated with slow flows). The ³H contents are more uniform with time (indicating an older age) and there is detectable natural radioactivity, because the waters have a longer residence time in the aquifers, which are diffuse flow systems.     

Aquifer geochemistry at potential aquifer storage and recovery sites in coastal plain aquifers in the New York city area,USA

The effects of injecting oxic water from the New York city (NYC) drinking-water supply and distribution system into a nearby anoxic coastal plain aquifer for later recovery during periods of water shortage (aquifer storage and recovery, or ASR) were simulated by a 3-dimensional, reactive-solute transport model. The Cretaceous aquifer system in the NYC area of New York and New Jersey, USA contains pyrite, goethite, locally occurring siderite, lignite, and locally varying amounts of dissolved Fe and salinity. Sediment from cores drilled on Staten Island and western Long Island had high extractable concentrations of Fe, Mn, and acid volatile sulfides (AVS) plus chromium-reducible sulfides (CRS) and low concentrations of As, Pb, Cd, Cr, Cu and U. Similarly, water samples from the Lloyd aquifer (Cretaceous) in western Long Island generally contained high concentrations of Fe and Mn and low concentrations of other trace elements such as As, Pb, Cd, Cr, Cu and U, all of which were below US Environmental Protection Agency (USEPA) and NY maximum contaminant levels (MCLs). In such aquifer settings, ASR operations can be complicated by the oxidative dissolution of pyrite, low pH, and high concentrations of dissolved Fe in extracted water.     

Growth mechanisms and geochemistry of carbonate concretions from the Cambrian Wheeler Formation (Utah,USA)

Carbonate concretions provide unique records of ancient biogeochemical processes in marine sediments. Typically, they form in organic‐rich mudstones, where a significant fraction of the bicarbonate required for carbonate precipitation is supplied from the decomposition of organic matter in the sediments. As a result, carbonates that comprise concretions are usually characterized by broad ranges in δ¹³C and include values that are significantly depleted relative to seawater. This article reports results from a physical, petrographic and geochemical analysis of 238 concretions from the Wheeler Formation (Cambrian Series 3), Utah, USA, which are unusual in several respects. Most prominently, they formed in organic‐poor mudstones (total organic carbon = 0·1 to 0·5%) and are characterized by a narrow range of δ¹³C that onlaps the range of contemporaneous seawater values. Subtle centre to edge trends in δ¹³C demonstrate that concretion precipitation was initiated by local chemical gradients set up by microbial activity in the sediments, but was sustained during growth by a large pool of inorganic bicarbonate probably derived from alkaline bottom waters. The large inorganic pool appears to have been important in facilitating rapid precipitation of the concretion matrix, which occurred via both displacive and replacive carbonate precipitation during early diagenesis. Stable isotope data from cogenetic pyrite (δ³⁴S) and silica (δ¹⁸O) phases provide insight into the evolution of biogeochemical processes during concretion growth, and suggest that concretions were formed almost entirely during sulphate reduction, with only minor modification thereafter. Concretions of the Wheeler Formation appear to represent an end‐member system of concretion formation in which rapid growth was promoted by ions supplied from sea‐water. As such, they offer insight into the spectrum of processes that may influence the growth of carbonate concretions in marine sediments.     

Helium and neon isotope geochemistry of some ground waters from the Canadian Precambrian Shield

Ground waters in a Precambrian granitic batholith at the Whiteshell Nuclear Research Establishment (WNRE) in Pinawa, Manitoba contain between 5 × 10^?5 and 10^?1 cc STP/g_H2O of radiogenic helium-4 but have relatively uniform ³He/⁴He ratios of between 0.6 × 10^?8 and 2.3 × 10³. The highest helium samples also contain radiogenic ^21,22Ne produced by (α,n) or (n,α) reactions with other isotopes. As much as 1.8 × 10^?9ccSTP/g_H2O of excess ²¹Ne and 3.8 × 10^?9ccSTP/gH₂O of excess ²²Ne have been measured. Helium and ²¹Ne ages of these ground waters, calculated on the basis of known crustal production rates of ⁴He and ²¹Ne, are unreasonably high (up to 2 × 10⁵ years) and incompatible with the ¹⁴C ages and other isotopic and hydrogeologic data. Uranium enrichment in the flow porosity of the granite may dominate ⁴He and ^21,22Ne production in this granite and mask the contributions from more typical U and Th concentrations in the rock matrix.At the Chalk River Nuclear Laboratories in Ontario helium concentrations in ground waters in a Precambrian monzonitic gneiss range from 1.5 × 10^?7 to 8.7 × 10^?4ccSTP/g_H2O with the ³He/⁴He ratios ranging from 2.0 × 10^?3 to 1.5 × 10^?7. The highest helium concentrations may be attributable to the presence of a thick uraniferous pegmatite vein and yield helium ages more than two orders of magnitude higher than the ¹⁴C ages. Application of He age dating equations to ground waters from Precambrian granitic rocks requires knowledge of the nature of uranium and thorium enrichment in the subsurface in order to select appropriate values for porosity and uranium and thorium concentration in the rock.     

Geochemical evolution of groundwater in carbonate aquifers in Taiyuan, northern China

Thirty-nine samples of both cold and thermal karst groundwater from Taiyuan, northern China were collected and analyzed with the aim of developing a better understanding of the geochemical processes that control the groundwater quality evolution in the region’s carbonate aquifers. The region’s karst groundwater system was divided into three geologically distinct sub-systems, namely, the Xishan Mountain karst groundwater subsystem (XMK), the Dongshan Mountain karst groundwater subsystem (DMK) and the Beishan Mountain karst groundwater subsystem (BMK). Hydrochemical properties of the karst groundwaters evolve from the recharge zones towards the cold water discharge zones and further towards the thermal water discharge zones. In the XMK and the DMK, the hydrochemical type of the groundwater evolves from HCO₃-Ca·Mg in the recharge - flow-through zone, to HCO₃·SO₄-Ca·Mg/SO₄·HCO₃-Ca·Mg in the cold water discharge zone, and further to SO₄-Ca·Mg in the thermal water discharge zone. By contrast, the water type changes from HCO₃-Ca·Mg to HCO₃·SO₄-Ca·Mg in the BMK, with almost invariable TDS and temperatures all along from the recharge to the discharge zone. The concentrations of Sr, Si, Fe, F⁻ and of some trace elements (Al, B, Li, Mn, Mo, Co, Ni) increase as groundwater temperature increases. Different hydrogeochemical processes occur in the three karst groundwater sub-systems. In the XMK and the DMK, the geochemical evolution of the groundwater is jointly controlled by carbonate dissolution/precipitation, gypsum dissolution and dedolomitization, while only calcite and dolomite dissolution/precipitation occurs in the BMK without dedolomitization. The hydrogeochemical data of the karst groundwaters were used to construct individual geochemical reaction models for each of the three different karst groundwater sub-systems. The modeling results confirm that dedolomization is the major process controlling hydrochemical changes in the XMK and the DMK. In the thermal groundwaters, the dissolution rates of fluorite, siderite and strontianite were found to exceed those of the cold karst groundwater systems, which can explain the higher concentrations of F⁻, Fe and Sr²⁺ that are found in these waters.     

Mixing of carbonate waters

When mineral solutions of different compositions are mixed, the molalities and activities of individual ions in the mixture are often non-linear functions of their end-member values. This non-linearity is particularly significant in determining mineral saturation levels. Mixtures of saturated solutions may be either undersaturated or supersaturated depending on the end-member compositions and the physical conditions in which end-members and their mixtures exist. In carbonate solutions important non-linear effects occur due to redistribution of carbonate species. In extreme cases this causes mixture pH to be below both the end-member pH values. A simple but precise computer program (WATMIX) has been developed for calculating mixture composition for closed and open system mixing of arbitrary end-members. A number of mixing examples are considered which allow one to isolate three important processes leading to non-linear behaviour: the algebraic effect, the δP_CO2 effect, and the ionic strength effect.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park,Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns.     

The influence of geology and land use on arsenic in stream sediments and ground waters in New England,USA

Population statistics for As concentrations in rocks, sediments and ground water differ by geology and land use features in the New England region, USA. Significant sources of As in the surficial environment include both natural weathering of rocks and anthropogenic sources such as arsenical pesticides that were commonly applied to apple, blueberry and potato crops during the first half of the 20th century in the region. The variation of As in bedrock ground water wells has a strong positive correlation with geologic features at the geologic province, lithology group, and bedrock map unit levels. The variation of As in bedrock ground water wells also has a positive correlation with elevated stream sediment and rock As chemistry. Elevated As concentrations in bedrock wells do not correlate with past agricultural areas that used arsenical pesticides on crops. Stream sediments, which integrate both natural and anthropogenic sources, have a strong positive correlation of As concentrations with rock chemistry, geologic provinces and ground water chemistry, and a weaker positive correlation with past agricultural land use. Although correlation is not sufficient to demonstrate cause-and-effect, the statistics favor rock-based As as the dominant regional source of the element in stream sediments and ground water in New England. The distribution of bedrock geology features at the geologic province, lithology group and map unit level closely correlate with areas of elevated As in ground water, stream sediments, and rocks.     

Review: Thermal water resources in carbonate rock aquifers

The current knowledge on thermal water resources in carbonate rock aquifers is presented in this review, which also discusses geochemical processes that create reservoir porosity and different types of utilisations of these resources such as thermal baths, geothermal energy and carbon dioxide (CO₂) sequestration. Carbonate aquifers probably constitute the most important thermal water resources outside of volcanic areas. Several processes contribute to the creation of porosity, summarised under the term hypogenic (or hypogene) speleogenesis, including retrograde calcite solubility, mixing corrosion induced by cross-formational flow, and dissolution by geogenic acids from deep sources. Thermal and mineral waters from karst aquifers supply spas all over the world such as the famous bath in Budapest, Hungary. Geothermal installations use these resources for electricity production, district heating or other purposes, with low CO₂ emissions and land consumption, e.g. Germany’s largest geothermal power plant at Unterhaching near Munich. Regional fault and fracture zones are often the most productive zones, but are sometimes difficult to locate, resulting in a relatively high exploration uncertainty. Geothermal installations in deep carbonate rocks could also be used for CO₂ sequestration (carbonate dissolution would partly neutralise this gas and increase reservoir porosity). The use of geothermal installations to this end should be further investigated.     

The geochemistry of iodine in near-shore carbonate sediments

The total concentration of I is commonly higher in surface terrigenous sediments relative to more deeply buried material. Diagenetic release, loss of dissolved I during burial, and back-reaction of I with the solid phase under oxidizing conditions contribute to I enrichment near the sediment/water interface. In order to differentiate between scavenging of dissolved I by organic matter or metal oxides, the diagenetic behavior of I was examined in the Fe-poor carbonate sediments of Florida Bay, Florida. In this environment I is released by organic decomposition at I/C ratios similar to terrigenous environments (~0.5 mmole/mole), transported to the oxygenated sediment/water interface, and lost to the overlying water. The dissolved I flux from these deposits is roughly equivalent to the production rate within the deposit (~10 μmole/m²/day at 28°C). No significant enrichment is observed in the solid phase.Dissolved iodine transport within the sediment column may also be controlled by non-steady-state lateral diffusion into burrows. These observations, together with laboratory experiments which demonstrate IO^?₃ scavenging by Fe-oxyhydroxides at pH ≤ 8, imply that enrichment of I in terrigenous surface sediments results predominantly from the initial oxidation of I^? to IO^?₃ by microorganisms, followed by sorption on Fe oxides. Upon burial and reduction during anaerobic decomposition, this metal-associated I is released to solution, in a manner similar to phosphate.     

Recharge and salination processes in the carbonate aquifers in Israel

Limestone and dolostone aquifers play a major role in the water supply system of Israel. In many cases, there are brackish to saline springs at their outlets. The source of the saline water and the mechanism of salinization differ from place to place. In some cases, it is due to mixing with seawater (Mediterranean or Dead Sea) at the fresh-saline water interface, while in other cases deepseated brines emerge along regional faults. The general policy for reclaiming the fresh component of the water before mixing with the saline component is to try to catch the fresh water as far as possible upstream from the outlet. In most cases, this is the area where the mixing takes place. The main case histories in Israel are discussed in this paper.     

Groundwater recharge in semi-arid carbonate aquifers under intensive use: the Estepa Range aquifers (Seville, southern Spain)

Quantifying groundwater recharge in carbonate aquifers located in semi-arid regions and subjected to intensive groundwater use is no easy task. One reason is that there are very few available methods suitable for application under such climatic conditions, and moreover, some of the methods that might be applied were originally designed with reference to non-carbonate aquifers. In addition, it is necessary to take into account the fact that, in any given aquifer, groundwater recharge is modified by the groundwater exploitation. Here we focus on four methods selected to assess their suitability for estimating groundwater recharge in carbonate aquifers affected by intensive exploitation. The methods were applied to the Estepa Range aquifers of Seville, southern Spain, which are subjected to different degrees of exploitation. Two conventional methods were used: chloride mass balance and daily soil–water balance. These results were compared with the results obtained by means of two non-conventional methods, designed for application to the carbonate aquifers of southern Spain: the APLIS and ERAS methods. The results of the different methods are analogous, comparable to those obtained in nearby non-exploited carbonate aquifers, confirming their suitability for use with carbonate aquifers in either natural or exploited regimes in a semi-arid climate.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.     

Estimating hydraulic conductivity from specific capacity for Hawaii aquifers,USA

Site-specific relationships between specific capacity and hydraulic parameters (transmissivity and hydraulic conductivity) were investigated for volcanic rocks in Maui, Hawaii, USA. Details about well construction were commonly ignored in previous studies. To improve on such efforts, specific-capacity values were normalized by the open interval of the well. Correcting specific capacity for turbulent head losses using step-drawdown tests and including aquifer penetration length improved the correlation between specific capacity and hydraulic conductivity and reduced uncertainty in the prediction of hydraulic parameters. The relationships provide estimates of aquifer parameters with correlation coefficients between 0.81 and 0.99. The relationships for Maui can probably be extended to other Hawaii islands, given the similarity of aquifer formations and a reasonable fit to step-drawdown data from Oahu. Hydraulic conductivity was estimated from 1,257 specific-capacity values in the Hawaii’s well database. Hydraulic-conductivity estimates for dike-free volcanic rocks are consistent on different islands. For all islands, the estimates range from 3 to 8,200 m/d, with a geometric-mean and median value of 272 and 291 m/d, respectively. A geostatistical approach was applied to Maui and Oahu to generate island-wide hydraulic-conductivity maps to facilitate groundwater management efforts.     

Stable carbon isotope ratios and the existence of a gas phase in the evolution of carbonate ground waters

The chemical and stable isotope compositions of unpolluted ground waters in carbonate terranes are a function of the pH, , ¹³C content of the ground water recharge, the ¹³C content of the carbonate rock, and the manner in which the rock is dissolved or precipitated. Physico-chemical models show that significantly different relationships exist between Ca²⁺ plus Mg²⁺, HCO₃^?, pH and ¹³C content of unpolluted ground waters when carbonate solution occurs in the presence or absence of a gas phase. A study was made of these relationships in waters from 21 springs and 13 wells in Nittany Valley, Pennsylvania. Assuming that CO₂ in the recharge zone has a ¹³C contents below ?21%. vs PDB, the data indicate that ground water flow to wells and springs, and carbonate rock solution probably occurs chiefly in the absence of a gas phase. This is in spite of the fact that most of such flow is under water table conditions. ¹³C contents averaged ?12·3%. for the spring waters and ?13·3%. for the well waters. Five well waters polluted by septic tank or sewage effluents had carbon isotopic compositions from ?13·5 to ?16·4%.,vs ?11·3 to?12·7 %. for the eight well waters relatively free of organic wastes.     

秦岭旬阳盆地下古生界钠长石岩岩石学和地球化学特征

热水沉积钠长石岩在南秦岭上古生界中颇具特点，与南秦岭众多的大型、超大型铅锌成矿关系密切。最近，在南秦岭旬阳盆地下古生界铅锌矿集区内的志留系梅子垭组地层中首次识别出一条近东西方向延伸长达10余千米的钠长石沉积岩带，与地层整合产出，渐变过渡，厚层块状、条带状、角砾状构造，均粒微-细晶结构、内碎屑结构；其化学成分以富含SiO2、Al2O3及Na2O为特征，富Fe、Mn，贫Co、Ni、Cu等微量元素；该钠长石岩的∑KEE、LKEE、HREE均较围岩偏低，具明显Eu亏损的特征。球粒陨石标准化配分曲线为右倾曲线。通过与秦岭泥盆纪热水沉积钠长石岩的岩相学及岩石化学对比，结合本区下古生界属于扬子北缘被动陆缘裂谷环境，初步认为这里下古生界钠长石岩可能属于热水沉积成因。