Crude oil in a shallow sand and gravel aquifer—II. Organic geochemistry

Crude oil spilled from a pipeline break in a remote area of north-central Minnesota has contaminated a shallow glacial outwash aquifer. Part of the oil was sprayed over a large area to the west of the pipeline and part of it accumulated in an oil body that floats at the water table to the east of the point of discharge. Total dissolved organic carbon (TDOC) concentrations in shallow groundwater collected in the oil spray area reach 16 mg/l. This is nearly an order of magnitude higher than the TDOC concentrations of native groundwater (∼2–3mg/l). The additional TDOC derives from the partial degradation of petroleum residues deposited at the land surface and transported to the aquifer by vertical recharge. In the vicinity of the oil body, TDOC concentrations in groundwater are 48 mg/l, 58% of the TDOC being composed of non-volatile organic C. The majority of the volatile DOC (63%) is a mixture of low-molecular-weight saturated, aromatic and alicyclic hydrocarbons derived from the oil. Downgradient from the oil body along the direction of groundwater flow, concentrations of all measured constituents of the TDOC pool decrease. Concentrations begin to decline most rapidly, however, in the zone where dissolved O₂ concentrations begin to increase, ∼50m downgradient from the leading edge of the oil. Within the anoxic zone near the oil body, removal rates of isometric monoaromatic hydrocarbons vary widely. This indicates that the removal processes are mediated mainly by microbiological activity. Molecular and spectroscopic characterization of the TDOC and its spatial and temporal variation provide evidence of the importance of biogeochemical processes in attenuating petroleum contaminants in this perturbed subsurface environment.     

Crude oil in a shallow sand and gravel aquifer—I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed ∼1 pH unit, and the concentrations of Ca, Mg and HCO₃⁻ increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO₂, Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO₂ precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix.The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.     

Dual impact on the groundwater aquifer in the Kazan Plain (Ankara, Turkey): sand–gravel mining and over-abstraction

This study explains the impact of sand–gravel mining and over-abstraction, and the response of the groundwater system in the Kazan Plain, Turkey. The plain used to be known for its fresh groundwater potential, valuable agricultural lands and natural beauty until the 1980s. According to the estimation in 1975, there was 15.5 million m³ annual useable freshwater in the Quaternary sand–gravel aquifer. Groundwater level ranged between 0 and 5 m from the surface of the plain in the 1970s. Because of the large and deep excavations by the sand–gravel pits during the past 25–30 years, the aquifer has thinned and removed entirely in some places. In addition, over-abstraction has accelerated the decline of the groundwater level, particularly in the middle and the upper part of the plain in recent years. As of 2009, about 12% of the total volume of the aquifer area removed by the pits and groundwater table has been reduced to between 5 and 20 m. The decline of the water table reaches 15–20 m in the regions where over-abstraction has taken place. To reduce the hazards to the groundwater system, the sand–gravel pits have to be banned immediately, a reclamation project applied and abstraction must be reduced.     

Is use of oil-field brine as a dust-abating agent really benign? Tracing the source and flowpath of contamination by oil brine in a shallow phreatic aquifer

In Ohio, 1985 H.R. Bill 501 authorizes the local authorities to issue permits to use oil-field brine surface spreading as a dust and ice control agent. Such permits are usually given without any necessary hydrogeological expertise as to the potential impact on the shallow aquifers, particularly if the brine spreading occurs in a recharge area. One such case occurred recently in the southwestern suburb of the City of Wooster, OH, USA, where a group of home owners were seeking judicial relief when their water wells began yielding salty water as a result of brine spreading on a nearby large open storage area for oil and gas well drilling supplies. The defendant, owner of the storage yard, acted in accordance with the permit issued by the local authorities. Yet, decentralized decision making and an increased emphasis on local and citizen involvement have created a gap between science and society. The local authorities were not required by law to condition the issuance of the permit on an analysis of the potential environmental impact. The decision to issue that permit was made purely on non-scientific grounds. Therefore, the residents had no choice but to embark on a costly process of proving the damages, causation, and liability in court of law. During the protracted, 6-year long conflict, an extensive hydrogeological and hydrochemical data set (including stable isotopes’ analyses along with the complete chemical analyses of major and minor constituents) was amassed at a great cost to both sides. The following article presents the hydrogeological and hydrochemical interpretation of this data set. In addition, the case illustrates a glaring deficiency in the Ohio, 1985 H.R. Bill 501, and one pitfall in the “politically correct” philosophy of delegating decision-making process entirely to the non-professional local authorities.     

Impact assessment of a saline waste lagoon on groundwater pollution near a coastal aquifer in India—synthesis of geoelectrical and hydrochemical studies

The present study is an attempt to assess the impact of a saline waste lagoon on the near subsurface through electrical resistivity tomography (ERT). Resistivity and IP imaging data have been collected on profiles close to the lagoon and at a far off location (control location). Water samples have been collected from the lagoon and a municipality drinking well close to it and analysed for the water chemistry. The geoelectrical sections indicate very low resistivity formations in the near subsurface in the vicinity of the lagoon as compared to the control profile. The water chemistry data from the monitoring well close to the profile also indicates very high total dissolved solids (8658 mg/L) and qualitatively supports the contamination of the near subsurface. The conductive formations in the vicinity of the lagoon can be attributed to the overflow from the lagoon or the seepage.     

The chemical evolution of Kurnub Group paleowater in the Sinai-Negev province—a mass balance approach

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO₂, smectite and degasses CO₂. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO₂. Concomitantly, there is precipitation of calcite, smectite, SiO₂ and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.     

Geochemical,isotopic and hydrological mass balance approaches to constrain the lake water–groundwater interaction in Dal Lake,Kashmir Valley

It is important to have qualitative as well as quantitative understanding of the hydraulic exchange between lake and groundwater for effective water resource management. Dal, a famous urban fresh water lake, plays a fundamental role in social, cultural and economic dynamics of the Kashmir Valley. In this paper geochemical, isotopic and hydrological mass balance approaches are used to constrain the lake water–groundwater interaction of Dal Lake and to identify the sources of lake water. Water samples of precipitation (n = 27), lake water (n = 18) and groundwater (n = 32) were collected across the lake and its catchment for the analysis of δ¹⁸O and δ²H. A total of 444 lake water samples and 440 groundwater samples (springs, tube wells and dug wells) were collected for the analysis of Ca²⁺, Mg²⁺, HCO₃ ^?, SO₄ ^2?, Cl^?, NO₃ ^?, Na⁺ and K⁺. Water table and lake water level were monitored at 40 observation locations in the catchment. Water table map including pH and EC values corroborate and verify the gaining nature of the Dal Lake. Stable isotopes of lake water in Boddal and Gagribal basins showed more deviation from the global meteoric water line than Hazratbal and Nigeen basins, indicating the evaporation of lake water. The isotopic and geochemical mass balance suggested that groundwater contributes a significant proportion (23–40%) to Dal Lake. The estimated average groundwater contribution to Dal Lake ranged from 31.2 × 10³ to 674 × 10³ m³ day^?1 with an average of 276 × 10³ m³ day^?1. The study will be useful to delineate the possible sources of nutrients and pollutants entering the lake and for the management of lake water resources for sustainable development.     

Review: groundwater management practices, challenges, and innovations in the High Plains aquifer, USA—lessons and recommended actions

The US High Plains aquifer, one of the largest freshwater aquifer systems in the world, continues to decline, threatening the long-term viability of the region’s irrigation-based economy. The eight High Plains States take different approaches to the development and management of the aquifer based on each state’s body of water laws that abide by different legal doctrines, on which Federal laws are superposed, thus creating difficulties in integrated regional water-management efforts. Although accumulating hydrologic stresses and competing demands on groundwater resources are making groundwater management increasingly complex, they are also leading to innovative management approaches, which are highlighted in this paper as good examples for emulation in managing groundwater resources. It is concluded that the fragmented and piecemeal institutional arrangements for managing the supplies and quality of water are inadequate to meet the water challenges of the future. A number of recommendations for enhancing the sustainability of the aquifer are presented, including the formation of an interstate groundwater commission for the High Plains aquifer along the lines of the Delaware and Susquehanna River Basins Commissions in the US. Finally, some lessons on groundwater management that other countries can learn from the US experience are outlined.     

Delineation of recharge patterns and contaminant transport using 3H–3He in a shallow aquifer contaminated by chlorinated solvents in South Korea

Stable isotopes of water and ³H–³He were used to delineate recharge patterns and contaminant transport for a granitic regolith aquifer in an industrial complex in Wonju, South Korea, that has historically been contaminated with chlorinated solvents including trichloroethene (TCE) and carbon tetrachloride (CT). Groundwater recharge mainly occurred in upgradient forested areas while little recharge occurred in the downgradient industrial areas covered with extensive sections of impermeable pavement and paddy fields. δ¹⁸O and δD data indicated that groundwater was mainly derived from summer precipitation. The apparent groundwater ages using ³H–³He ranged from 1 to 4 yrs in the upgradient area and from 9 to 10 yrs in the downgradient area. Comparison of groundwater flow velocities based on Darcy’s law and those calculated with simple mass balance models and groundwater age supported the presence of preferential pathways for TCE movement in the study area. Measureable TCE was observed in groundwater irrespective of groundwater age. Considering the 3-yr duration of the TCE spill, 14 yrs before sampling, this indicates that TCE plumes were continuously fed from sources in the unsaturated zone after the spill ended and moved downgradient without significant degradation in the aquifer.     

A comparative study of shallow groundwater level simulation with WA–ANN and ITS model in a coastal island of south China

Accurate and reliable prediction of shallow groundwater level is a critical component in water resources management. Two nonlinear models, WA–ANN method based on discrete wavelet transform (WA) and artificial neural network (ANN) and integrated time series (ITS) model, were developed to predict groundwater level fluctuations of a shallow coastal aquifer (Fujian Province, China). The two models were testified with the monitored groundwater level from 2000 to 2011. Two representative wells are selected with different locations within the study area. The error criteria were estimated using the coefficient of determination (R ²), Nash–Sutcliffe model efficiency coefficient (E), and root-mean-square error (RMSE). The best model was determined based on the RMSE of prediction using independent test data set. The WA–ANN models were found to provide more accurate monthly average groundwater level forecasts compared to the ITS models. The results of the study indicate the potential of WA–ANN models in forecasting groundwater levels. It is recommended that additional studies explore this proposed method, which can be used in turn to facilitate the development and implementation of more effective and sustainable groundwater management strategies.     

Foreign inclusions in stony meteorites—III. Rare gases and oxygen isotopes in a carbonaceous chondritic xenolith in the Plainview gas-rich chondrite

Measurements of oxygen and rare gas isotopes in a carbonaceous xenolithic inclusion in the Plainview H5 chondrite indicate that the xenolith and Plainview host are of two distinct meteorite types, and that no isotopic exchange has taken place between the two materials since their juxtaposition. The oxygen isotope analysis of the xenolith yields δ-¹⁸O value of 6.5 ± 0.1 % relative to SMOW, a value similar to that of carbonaceous chondrites (C2). Rare gas contents of the xenolith are also similar to those of carbonaceous chondrites. The radiation ages of the xenolith ($\text{2.9 ± 0.4}\text{Myr}$) and the host ($\text{2.8 ± 0.4}\text{Myr}$) are identical.Analyses of the rare gases in a sample of the host material adjacent to the xenolith show that Plainview is gas-rich, i.e., it contains large amounts (52,300 ± 10^?8 cm³ STP/g ⁴He) of solar-type trapped gases.We speculate that carbonaceous chondritic material may be more prevalent in the asteroid belt than previously suspected.     

Stochastic continuum modeling of flow and transport in a crystalline rock mass: Fanay-Augères,France, revisited

A stochastic discrete-fracture model was used by Cacas et al.^a,b to interpret flow measurements and transport experiments in a fractured crystalline rock mass at Fanay-Augères. They considered continuum models to be incapable of properly interpreting small-scale measurements or tracer tests in fractured systems, which, in their view, require three-dimensional modeling of numerous discrete channels; in their opinion, continuum modeling applies only to average flow on a relatively large scale. Cacas et al. considered their discrete fracture model to have been validated by its demonstrated ability to reproduce selected experimental results. In this paper, flow and transport at Fanay-Augères are modeled by viewing the fractured rock as a stochastic continuum in a manner originally proposed by Neuman^c,d. The stochastic continuum approach obviates the need for detailed information about fracture geometry or assumptions about how individual fractures control flow and transport. All it requires is the delineation of a few dominant features, which can be embedded into the stochastic continuum model as heterogeneous porous slabs. Though a fault zone has been identified at the Fanay-Augères experimental site, it has been modeled neither by Cacas et al. nor in this paper. In fact, in this paper, a larger selection of experimental results than those considered by Cacas et al. are reproduced merely by modeling the rock as a statistically homogeneous continuum in two dimensions. These results demonstrate that a continuum approach may be well suited for the analysis of flow and transport in fractured rock. This does not constitute a validation of the continuum approach, just as the results of Cacas et al. fall short of validating the discrete fracture approach. Instead, the two sets of results illustrate jointly the well-established principle that an open system, especially one as complex as fractured hydrogeologic environments tend to be, cannot be described uniquely on the basis of sparse data and need not be described in great detail to capture its salient behavior by a model.^a Cacas MC, Ledoux E, de Marsily G, Barbreau A, Calmels P, Gaillard B, Margritta R (1990a) Modelling fracture flow with a stochastic discrete fracture network: calibration and validation. 1. The flow model. Water Resour Res 26(3):479–489^b Cacas MC, Ledoux E, de Marsily G, Barbreau A, Calmels P, Gaillard B, Margritta R (1990b) Modelling fracture flow with a stochastic discrete fracture network: calibration and validation. 2. The transport model. Water Resour Res 26(3):491–500^c Neuman SP (1987) Stochastic continuum representation of fractured rock permeability as an alternative to the REV and fracture network concepts, in Rock Mechanics. In: Farmer IW, Daemen JJK, Desai CS, Glass CE, Neuman SP (eds) Proceedings of the 28th U.S. Symposium, Tucson, Arizona. Balkema, Rotterdam, pp 533–561^d Neuman SP (1988) A proposed conceptual framework and methodology for investigating flow and transport in Swedish crystalline rocks. SKB Swedish Nuclear Fuel and Waste Management Co., Stockholm, September, Arbetsrapport 88–37, 39 pp     

Trace metals in suspended particulate matter and in sediment trap material from a permanently anoxic fjord — Framvaren, South Norway

Geochemical studies of the trace metal concentrations in suspended particulate matter (SPM) and sediment trap material from a permanently anoxic fjord, Framvaren, South Norway in 1989 and 1993 indicate that extremely high concentrations of zinc (max = 183920 mg/kg), copper (max = 4130 mg/kg), lead (max = 2752 mg/kg), and cadmium (max= 8.1 mg/kg) sometimes (1993) occur in the SPM collected in the anoxic water layer. The highest concentrations of Zn occur just below the redoxcline at 22 m water depth (in 1993), and copper, lead and cadmium have maximum concentrations between 30 and 80 m depth, where the amount of total SPM is at a minimum (about 0.3 mg/L). On a mass per volume (g/L) basis, the maximum concentrations of Cd, Cu and Fe occur at the interface (21m) and those of Zn occur just below the redoxcline (22 m depth). The SPM and sediment trap data suggest that the metals are precipitated as sulfide minerals in the anoxic water. The presence of particulate sulfides was confirmed by SEM studies that show the occurrence of discrete metal (Cu, Fe, Pb, and Zn) sulfide particles in size from 10–20 m as well as framboidal pyrites (1–5 m in size). Higher levels of metal sulfides at intermediate depths rather than in the deep water of Framvaren (> 100 m), may be due to input of trace metals by water exchange over the sill in the upper part of the water column. In the deep water, less metal sulfide precipitation takes place due to depletion of trace metals, and the dilution of particulate metal concentrations by organic matter and by the chemogenic formation of calcite.     

Variation in groundwater levels and water quality in Chhatna Block, Bankura district, West Bengal — a GIS approach

Ground water levels and quality in Chhatna Block of West Bengal were studied based on different indices for irrigation and drinking purposes. A detailed hydrogeological investigation was carried out to have an overall idea of the aquifer system of the area. The ground water occurs under shallow to moderately deep water table condition. The groundwater is stored mostly in the weathered residuum and fractured — hard rock. Sodium absorption ratio (SAR), soluble sodium percentage (SSP), residual sodium bi-carbonate (RSBC), electrical conductance (EC), magnesium adsorption ratio (MAR) Kelly’s ratio (KR), total hardness (TH), permeability index (PI) were calculated as derived parameters, to investigate the ionic toxicity. From the results of chemical analysis, it was revealed that the values of Sodium Adsorption Ratio indicate that, ground water of the area falls under the category of low sodium hazard. So, there was neither salinity nor toxicity problem of irrigation water, and hence the ground water can safely be used for long-term irrigation. Plotting of analytical results of the groundwater collected from different areas in Piper’s trilinear diagram (1944) indicate that, the waters of the study area fall under fresh and sulphate rich region of the rhombus.     

Groundwater flow in a transboundary fault-dominated aquifer and the importance of regional modeling: the case of the city of Querétaro,Mexico

The city of Querétaro, located near the political boundary of the Mexican states of Querétaro and Guanajuato, relies on groundwater as it sole water supply. Groundwater extraction in the city increased from 21?×?10⁶ m³/yr in 1970 to 104?×?10⁶ m³/yr in 2010, with an associated drawdown of 100 m in some parts of the aquifer. A three-dimensional numerical groundwater-flow model has been developed that represents the historical evolution of the aquifer’s potentiometric levels and is used to simulate the effect of two scenarios: (1) a 40 % reduction in the extraction rate from public water supply wells in early 2011 (thus reducing the extraction to 62?×?10⁶ m³/yr), and (2) a further reduction in 2021 to 1?×?10⁶ m³/yr. The modeling results project a temporary recovery of the potentiometric levels after the 40 % reduction of early 2011, but a return to 2010 levels by 2020. If scenario 2 is implemented in 2021, the aquifer will take nearly 30 years to recover to the simulated levels of 1995. The model also shows that the wells located in the city of Querétaro started to extract water from part of the aquifer beneath the State of Guanajuato in the late 1970s, thus showing that the administrative boundaries used in Mexico to study and develop water resources are inappropriate, and consideration should be given to physical boundaries instead. A regional approach to studying aquifers is needed in order to adequately understand groundwater flow dynamics.     

Hydrochemistry of groundwater in a coastal region and its repercussion on quality,a case study—Thoothukudi district,Tamil Nadu,India

A hydrogeochemical study was conducted in Thoothukudi district situated in the southeast coast of Tamil Nadu, India to identify the influence of saltwater intrusion and suitability of groundwater for domestic and agricultural purposes. Scattered studies of this coastal region have reported signs of seawater intrusion, salt pan and industrial activity together with natural weathering process. To have a holistic picture of geochemical processes in the entire district, a total of 135 groundwater samples were collected and analyzed for major cations and anions. The geochemical parameters were compared with world and Indian standards and it was found that most samples are unsuitable for drinking purpose. The geochemical facies of the groundwater showed Na–Cl as the dominant water type indicating the saline nature of the groundwater. Chadda’s plots show that most of the samples fall in the Na–Cl type of water due to seawater intrusion. The samples were classified with parameters like sodium absorption ratio, residual sodium carbonate, total hardness, chloride, index to base exchange, electrical conductivity and facies to determine their suitability for irrigation purpose. It was inferred that the samples falling along the coast are not suitable for the irrigation purpose. The seawater-mixing percentage indicates that strong mixing was observed in the near shore and at the proximity of the salt pan. The permanent hardness was predominant in all the samples compared to the carbonate hardness reducing its domestic usability.