The development and control of the land subsidence in the Yangtze Delta,China

Land subsidence in China occurs predominantly in 17 provinces (cities) situated in the eastern and middle regions of the country, including Shanghai, Tianjin and Jiangsu, and Hebei provinces. It is primarily caused by groundwater overpumping. One of the areas most severely affected by land subsidence is the Yangtze Delta, most of which consists of Shanghai City, the Su-Xi-Chang area (Suzhou, Wuxi and Changzhou cities) of Jiangsu Province, and the Hang-Jia-Hu area (Hangzhou, Jiaxing and Huzhou cities) of Zhejiang Province. The excessive exploitation of groundwater forms in a large regional cone of depression and, consequently, land subsidence is also regional, currently centered in the Shanghai and Su-Xi-Chang areas. In 2002, the maximum cumulative subsidence of Shanghai, Su-Xi-Chang and Hang-Jia-Hu were 2.63 m, 2.00 and 1.06 m, respectively. The land subsidence area is continuing to expand throughout the Yangtze Delta. To study the characteristics and the pattern of this land subsidence, the government has implemented a monitoring system involving the placement of 37 groups of extensometers (layers marks) and drilling of more than 1000 observation wells. These provide an invaluable historical record of deformation and pore water pressure and facilitate studies on the special features of soil deformation when the groundwater level changes due to pumping. Several measures have been taken in recent years to control the development of the land subsidence in the different areas; these include groundwater injection, prohibition of pumping deep confined groundwater, and an adjustment of the pumping depth and magnitude of the groundwater withdrawn. At present, although the subsidence area is still increasing slowly, the subsidence rate is controlled.     

苏锡常地区非线性地面沉降耦合模型研究

长期过量开采地下水所引发的地面沉降是一个复杂的非线性变化过程,对其进行数值模拟时,如不考虑沉降发展过程中模型参数的非线性变化,会给预测带来很大误差。本文依据苏锡常地区实际资料,通过典型钻孔土力学试验,确定出土体在不同荷载条件下的弹塑性和蠕变特征方程以及土体渗透系数随孔隙度变化的关系式。在此基础上建立了研究区三维变系数地下水流模型及考虑土体垂向不同变化特征(弹塑变或蠕变)的一维区域沉降模型,并采用多尺度有限单元法对模型进行了真正意义上的耦合求解。     

Regional land subsidence simulation in Su-Xi-Chang area and Shanghai City, China

Su-Xi-Chang area and Shanghai City, located in the south of Yangtze Delta, China, has subsided due to groundwater overpumping. Because of the regional scale of the groundwater exploitation, cone of depression and land subsidence at present, Su-Xi-Chang area and Shanghai City are treated as a single area for land subsidence study to avoid the uncertainty of boundary condition due to the regionalism. The characteristics of aquifer system compaction are complex because of the difference in the types, compositions and structures of the soils that the hydrostratigraphic units are composed of, and in the histories of groundwater level change the hydrostratigraphic units have experienced. Considering the fact that different hydrostratigraphic units have different kinds of deformation and that an identical unit may also present different deformation characteristics, such as elasticity, elasto-plasticity, and visco-elasto-plasticity, at different sites of the cone of depression or in different periods, corresponding constitutive laws have been adopted. This avoids the shortcomings of the previous research that the same constitutive law was adopted in all the hydrostratigraphic units during the entire time period. A coupled flow and subsidence model, which includes a three-dimensional flow model with variable coefficients and a one-dimensional (vertical) subsidence model, is built according to the complicated hydrological condition in the region. The simulation model is calibrated using observed data, which include compression of individual strata from groups of extensometers and groundwater levels from observation wells from 1995 to 2002. The model reproduced that the primary subsidence layer in Shanghai shifts from the shallow aquitard to the fourth confined aquifer because of the groundwater yield variations and the change of exploitation aquifers. However the third aquitard was the primary subsidence layer in Su-Xi-Chang area and the compaction deformation of the sandy aquifers was remarkable. The simulation results could provide some reasonable advice about groundwater exploitation in the future.     

Numerical simulation of land subsidence induced by groundwater overexploitation in Su-Xi-Chang area,China

Su-Xi-Chang area is one of the typical regions in China which suffers from severe land subsidence. Various field monitoring records were integrated to study the characteristics and mechanisms of land subsidence in this region. The development of the land subsidence in this region shows a tight spatial and temporal correlation with the groundwater pumping. Based on the analysis of the field data, it is found that the deformation patterns of the hydrogeologic units are greatly related to the hydrogeologic properties and groundwater level variations. Some have an elastic behavior, others may have an elastic–plastic rheology. Hence, a 3D finite element numerical model considering the rheological properties of the soil was developed to simulate the groundwater level and land subsidence. Both hydraulic conductivity and specific storage were expected to vary with the porosity during the process of consolidation. Multiscale finite element method (MsFEM) was applied to solve the model during the period from 1996 to 2004. After calibrating the model with the observed groundwater level and subsidence data, the parameters of the multi-layers system were estimated. The calibrated model outputs fit reasonably well with the observed data. Consequently the model can be applied to predict groundwater level and land subsidence in future pumping scenarios. The model predictive results show that land subsidence rate can be controlled and even rebound may occur after the implementation of the groundwater exploitation prohibition. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Behaviour of boron and strontium isotopes in groundwater–aquifer interactions in the Cornia Plain (Tuscany,Italy)

The Cornia Plain alluvial aquifer, in Tuscany, is exploited intensely to meet the demand for domestic, irrigation and industrial water supplies. The B concentration of groundwater, however, is often above the European limit of 1 mg L⁻¹, with the result that exploitation of these water resources requires careful management. Boron and Sr isotopes have been used as part of a study on the origin and distribution of B dissolved in groundwater, and indirectly as a contribution to the development of appropriate water management strategies.The geochemistry of the Cornia Plain groundwater changes from a HCO₃ facies in the inland areas to a Cl facies along the coastal belt, where seawater intrusion takes place. The B concentration of groundwater increases towards the coastal areas, while the ¹¹B/¹⁰B ratio decreases. This indicates that there is an increasing interaction between dissolved B and the sediments forming the aquifer matrix, whose B content is in the order of 100 mg kg⁻¹. Adsorption–desorption exchanges take place between water and the sediment fine fraction rich in clay minerals, with a net release of B from the matrix into the groundwater, and a consequent δ¹¹B shift from positive to negative values. The aquifer matrix sediments therefore seem to be the major source of B dissolved in the groundwater.The groundwater–matrix interactions triggered by the ionic strength increase caused by seawater intrusion can also be detected in the Ca–Na ion exchanges. Dissolved Sr follows a trend similar to that of Ca, while the ⁸⁷Sr/⁸⁶Sr ratio is equal to that of the exchangeable Sr of the aquifer matrix and therefore does not change significantly.These results have helped to define a new strategy for groundwater exploitation, with the final objective of reducing B concentration in the water extracted from the aquifer.     

A conceptual framework of groundwater flow in some crystalline aquifers in Southeastern Ghana

A conceptual groundwater flow model was developed for the crystalline aquifers in southeastern part of the Eastern region, Ghana. The objective was to determine approximate levels of groundwater recharge, estimate aquifer hydraulic parameters, and then test various scenarios of groundwater extraction under the current conditions of recharge. A steady state groundwater flow model has been calibrated against measured water levels of 19 wells in the area. The resulting recharge is estimated to range from 8.97 × 10^?5 m/d to 7.14 × 10^?4 m/d resulting in a basin wide average recharge of about 9.6% of total annual precipitation, which results in a basin wide quantitative recharge of about 2.4 million m³/d in the area. This compares to recharge estimated from the chloride mass balance of 7.6% of precipitation determined in this study. The general groundwater flow in the area has also been determined to conform to the general northeast–southwest structural grain of the country. The implication is that the general hydrogeology is controlled by post genetic structural entities imposed on the rocks to create ingresses for sufficient groundwater storage and transport. Calibrated aquifer hydraulic conductivities range between 0.99 m/d and over 19.4 m/d. There is a significant contribution of groundwater discharge to stream flow in the study area. Increasing groundwater extraction will have an effect on stream flow. This study finds that the current groundwater extraction levels represent only 0.17% of the annual recharge from precipitation, and that groundwater can sustain future increased groundwater demands from population growth and industrialization.     

Is 222Rn a suitable tracer of stream–groundwater interactions? A case study in central Italy

River water infiltration into an unconfined porous aquifer (∼73% gravels, ∼12% sands, ∼15% silts and clays) in the Petrignano d’Assisi plain, central Italy, was traced combining isotopic techniques (²²²Rn) with hydrochemical and hydrogeologic techniques in order to characterize the system under study. The ²²²Rn gave information about the river water residence times within the aquifer and hydrochemical data, in a two-component mixing model, which allowed estimating the extent of mixing between surface waters and groundwater in wells at increasing distances from the river. The mixing measured in the well closer to the riverbank indicated a higher contribution of river water (up to 99%) during the groundwater recession phase and a moderate contribution (up to 64%) during the recharge phase. A model describing ²²²Rn concentrations in groundwater as the result of both parent/daughter nuclide equilibrium and mixing process (²²²Rn mixing/saturation model) was used to describe observed Rn concentrations and mixing index trends with the aim of evaluating water mean infiltration velocities along the transect. The stream bank infiltration velocities obtained by the model ranged from 1 m day⁻¹ during groundwater recharge periods, when river water infiltration is lower, to 39 m day⁻¹ during recession phases, when river water infiltration is larger.     

Groundwater fluxes into a submerged sinkhole area,Central Italy,using radon and water chemistry

The groundwater contribution into Green Lake and Black Lake (Vescovo Lakes Group), two cover collapse sinkholes in Pontina Plain (Central Italy), was estimated using water chemistry and a ²²²Rn budget. These data can constrain the interactions between sinkholes and deep seated fluid circulation, with a special focus on the possibility of the bedrock karst aquifer feeding the lake. The Rn budget accounted for all quantifiable surface and subsurface input and output fluxes including the flux across the sediment–water interface. The total value of groundwater discharge into Green Lake and Black Lake (∼540 ± 160 L s⁻¹) obtained from the Rn budget is lower than, but comparable with historical data on the springs group discharge estimated in the same period of the year (800 ± 90 L s⁻¹). Besides being an indirect test for the reliability of the Rn-budget “tool”, it confirms that both Green and Black Lake are effectively springs and not simply “water filled” sinkholes. New data on the water chemistry and the groundwater fluxes into the sinkhole area of Vescovo Lakes allows the assessment of the mechanism responsible for sinkhole formation in Pontina Plain and suggests the necessity of monitoring the changes of physical and chemical parameters of groundwater below the plain in order to mitigate the associated risk.     

Chloride imbalance in a catchment undergoing hydrological change: Upper Barwon River,southeast Australia

Documenting whether surface water catchments are in net chemical mass balance is important to understanding hydrological systems. Catchments that export significantly greater volumes of solutes than are delivered via rainfall are not in hydrologic equilibrium and indicate a changing hydrological system. Here an assessment is made of whether a saline catchment in southeast Australia is in chemical mass balance based on Cl. The upper reaches of the Barwon River, southeast Australia, has total dissolved solids, TDS, concentrations of up to 5860 mg/L and Cl concentrations of up to 3370 mg/L. The high river TDS concentrations are due to the influxes of groundwater with TDS concentrations of up to 68,000 mg/L. Between 1989 and 2011, the median annual Cl flux from the upper Barwon catchment was 17.8 × 10⁶ kg (∼140 kg/a/ha). This represents 340–2230% of the annual Cl input by rainfall to the catchment. Major ion and stable isotope geochemistry indicate that the dominant source of solutes in the catchment is evapotranspiration of rainfall, precluding mineral dissolution as a source of excess Cl. The upper Barwon catchment is not in chemical mass balance and is a net exporter of solutes. The chemical imbalance may reflect the transition within the last 100 ka from an endorheic lake system where solutes were recycled producing shallow groundwater with high TDS concentrations to a better drained catchment. Alternatively, a rise in the regional water table following land clearing may have increased the input of groundwater with high TDS concentrations to the river system.     

Groundwater flow system under a rapidly urbanizing coastal city as determined by hydrogeochemistry

In the Jakarta area (Indonesia), excessive groundwater pumping due to the rapidly increasing population has caused groundwater-related problems such as brackish water contamination in coastal areas and land subsidence. In this study, we adopted multiple hydrogeochemical techniques to demonstrate the groundwater flow system in the Jakarta area. Although almost all groundwater existing in the Jakarta basin is recharged at similar elevations, the water quality and residence time demonstrates a clear difference between the shallow and deep aquifers. Due to the rapid decrease in the groundwater potential in urban areas, we found that the seawater intrusion and the shallow and deep groundwaters are mixing, a conclusion confirmed by major ions, Br^?:Cl^? ratios, and chlorofluorocarbon (CFC)-12 analysis. Spring water and groundwater samples collected from the southern mountainside area show younger age characteristics with high concentrations of ¹⁴C and Ca–HCO₃ type water chemistry. We estimated the residence times of these groundwaters within 45 years under piston flow conditions by tritium analysis. Also, these groundwater ages can be limited to 20–30 years with piston flow evaluated by CFCs. Moreover, due to the magnitude of the CFC-12 concentration, we can use a pseudo age indicator in this field study, because we found a positive correlation between the major type of water chemistry and the CFC-12 concentration.     

Paleo water–rock interaction determined through isotopic tracing (Sr,O, C,U) in fracture-fill minerals: Evidence from the Vienne granitoids (France)

Based on the concepts (a) that the stable C and O isotopes combined with the Sr isotope ratios of fracture fills should reflect the source groundwater from which the solid phases precipitated and (b) that U-series disequilibria (USD) enable the calculation of residence time for the U by using Fe oxides as the best candidate, an “isotopic toolbox” was applied to fracture fill from the crystalline basement of the Vienne district. The fracture fills are formed mainly of carbonates, clays and Fe oxides. The isotope data indicate two main generations of carbonate that originated from hydrothermal circulation and equilibrium with present-day groundwaters but the Sr isotope ratios highlight another component with a higher ⁸⁷Sr/⁸⁶Sr ratio reflecting the complexity of the water–rock interactions.For the USD, the Fe-hydroxides located at 207 m depth yield an age of 102 ± 5 ka (St. Germain I interglacial stage), whereas those located at 277 m and 300 m yield respective ages of 173 ± 15 ka and 181 ± 10 ka. These corresponding to the transition between the penultimate glacial period (isotopic stage 6) and the end of the preceding interglacial stage (isotopic sub-stage 7a). Investigating water–rock interaction (⁸⁷Sr/⁸⁶Sr, ¹⁸O, ¹³C, USD) in the fracture-fill minerals from the crystalline basement has shown that such an approach is relevant to developing an understanding of how the groundwater system has changed over time.     

Hydrogeochemical evolution of confined groundwater in northeastern Osaka Basin,Japan: estimation of confined groundwater flux based on a cation exchange mass balance method

A confined aquifer system has developed in argillaceous marine and freshwater sediments of Pliocene–Holocene age in the northeastern Osaka Basin (NEOB) in central Japan. The shallow groundwater (<100 m) in the system is recharged in a northern hilly to mountainous area with dominantly Ca-HCO₃ type water, which changes as it flows toward the SW to Mg-HCO₃ type and then to Na-HCO₃ type water. Comparison of the chemical and Sr isotopic compositions of the groundwater with those of the bulk and exchangeable components of the underground sediments indicates that elements leached from the sediments contribute negligibly to the NEOB aquifer system. Moreover, model calculations show that contributions of paleo-seawater in the deep horizon and of river water at the surface are not major factors of chemical change of the groundwater. Instead, the zonal pattern of the HCO₃-dominant groundwater is caused by the loss of Ca²⁺ from the water as it is exchanged for Mg²⁺ in clays, followed by loss of Mg + Ca as they are exchanged for Na + K in clays between the Ca-HCO₃ type recharge water and the exchangeable cations in the clay layers, which were initially enriched in Na⁺. Part of this process was reproduced in a chromatographic experiment in which Na type water with high ⁸⁷Sr/⁸⁶Sr was obtained from Mg type water with low ⁸⁷Sr/⁸⁶Sr by passing it through marine clay packed in a column. The flux of recharge water into the confined aquifer system according to this chromatographic model is estimated to be 0.99 mm/day, which is compatible with the average recharge flux to unconfined groundwater in Japan (1 mm/day).     

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer,Leetown Science Center,West Virginia,USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from ³H/³He and SF₆ data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg⁻¹), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The ³H/³He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF₆ and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.     

Metal mobility by de-icing salt from an infiltration trench for highway runoff

Soil from an infiltration trench for highway runoff was leached in columns alternately with NaCl and de-ionised water to simulate the runoff of de-icing salt into the trench followed by snowmelt or rainwater. Simultaneously, two columns with the same soil were leached with de-ionised water throughout the experiment. In addition, the groundwater below the infiltration trench was sampled on some occasions. The column leachate and groundwater were split into two sub samples, one was filtered though a 0.45 μm filter; both were analysed for Pb, Cd, Zn, Fe and total organic carbon (TOC). The column experiment showed clearly that an extensive mobilisation of Pb occurred in low electrolyte water leaching following NaCl leaching. The high Pb concentration coincided with peaks in Fe and TOC concentrations and implied colloid-assisted transport. Conversely, Cd and Zn concentrations were raised in the NaCl leachate and a high correlation with Cl showed that Cl complexes are important for the mobilisation, although a pH effect and ionic exchange cannot be excluded. Only 0.15% and 0.06% of the total amount of Pb was leached from the columns leached with alternating NaCl and deionised water confirming the usual hypotheses about the high immobility of Pb in soils. However, on one occasion when the ionic strength and pH was the lowest measured the concentration of Pb in groundwater sampled from 2.5 m depth was 27 μg L⁻¹ in the dissolved phase (<0.45 μm) and 77 μg L⁻¹ in the particle phase (>0.45 μm). These Pb concentrations are almost 3 and 8 times above the Swedish limit for drinking water quality. Accordingly, in spite of the immobility of Pb the accumulation in roadside soils is so large that groundwater quality is threatened. In conclusion, the study suggests that roadside soils impacted by NaCl from de-icing operations contribute Pb to groundwater by colloid-assisted transport.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Spatial variations in water composition at a northern Canadian lake impacted by mine drainage

Release of acid drainage from mine-waste disposal areas is a problem of international scale. Contaminated surface water, derived from mine wastes, orginates both as direct surface runoff and, indirectly, as subsurface groundwater flow. At Camp Lake, a small Canadian Shield lake that is in northern Manitoba and is ice-covered 6 months of the year, direct and indirect release of drainage from an adjacent sulfide-rich tailings impoundment has severely affected the quality of the lake water. Concentrations of the products from sulfide oxidation are extremely high in the pore waters of the tailings impoundment. Groundwater and surface water derived from the impoundment discharge into a semi-isolated shallow bay in Camp Lake. The incorporation of this aqueous effluent has altered the composition of the lake water, which in turn has modified the physical limnology of the lake. Geochemical profiles of the water column indicate that, despite its shallow depth (6 m), the bay is stratified throughout the year. The greatest accumulation of dissolved metals and SO₄ is in the lower portion of the water column, with concentrations up to 8500 mg L⁻¹ Fe, 20,000 mg L⁻¹ SO₄, 30 mg L⁻¹ Zn, 100 mg L⁻¹ Al, and elevated concentrations of Cu, Cd, Pb and Ni. Meromictic conditions and very high solute concentrations are limited to the bay. Outside the bay, solute concentrations are lower and some stratification of the water column exists. Identification of locations and composition of groundwater discharge relative to lake bathymetry is a fundamental aspect of understanding chemical evolution and physical stability of mine-impacted lakes.     

Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ³⁴S_SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ¹⁸O_SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ³⁴S_SO4 and δ¹⁸O_SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II₁) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II₂) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II₃) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ³⁴S_SO4 = 10–35‰ and δ¹⁸O_SO4 = 7–20‰), soil sulfate (δ³⁴S_SO4 = 5.9‰ and δ¹⁸O_SO4 = 5.8‰) and sewage water (δ³⁴S_SO4 = 10.0‰ and δ¹⁸O_SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II₃), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ³⁴S_SO4 and δ¹⁸O_SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.     

Combining boron isotopes and carbamazepine to trace sewage in salinized groundwater: A case study in Cap Bon,Tunisia

The Korba aquifer on the east coast of Cape Bon has been overexploited since the 1960s with a resultant reversal of the hydraulic gradient and a degradation of the quality due to seawater intrusion. In 2008 the authorities introduced integrated water resources planning based on a managed aquifer recharge with treated wastewater. Water quality monitoring was implemented in order to determine the different system components and trace the effectiveness of the artificial recharge. Groundwater samples taken from recharge control piezometers and surrounding farm wells were analyzed for their chemical contents, for their B isotopes, a proven tracer of groundwater salinization and domestic sewage, and their carbamazepine content, an anti-epileptic known to pass through wastewater treatment and so recognized as a pertinent tracer of wastewater contamination. The system equilibrium was permanently disturbed by the different temporal dynamics of continuous processes such as cation exchange, and by threshold processes linked to oxidation–reduction conditions. The B isotopic compositions significantly shifted back-and-forth due to mixing with end-members of various origin. Under the variable contribution of meteoric recharge, the Plio-Quaternary groundwater (δ¹¹B of 35–40.6‰, a mean B concentration of 30 μmol/L, no carbamazepine, n = 7) was subject to seawater intrusion that induced a high δ¹¹B level (δ¹¹B of 41.5–48.0‰, a mean B concentration of 36 μmol/L, and n = 8). Fresh groundwater (δ¹¹B of 19.89‰, B concentration of 2.8 μmol/L, no carbamazepine) was detected close to the recharge site and may represent the deep Miocene pole which feeds the upper Plio-Quaternary aquifer. The managed recharge water (δ¹¹B of 10.67–13.8‰, n = 3) was brackish and of poor quality with a carbamazepine content showing a large short term variability with an average daily level of 328 ± 61 ng/L. A few piezometers in the vicinity of the recharge site gradually acquired a B isotopic composition close to the wastewater signature and showed an increasing carbamazepine content (from 20 to 910 ng/L). The combination of B isotopic signatures with B and carbamazepine contents is a useful tool to assess sources and mixing of treated wastewaters in groundwaters. Effluent quality needs to be greatly improved before injection to prevent further degradation of groundwater quality.     

Arsenic and other drinking water quality issues,Muzaffargarh District,Pakistan

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L⁻¹ in 58% of samples and reached up to 906 μg L⁻¹. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L⁻¹. In fact, in rural areas, concentrations stay below 25 μg L⁻¹ because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L⁻¹ As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.     

Monitoring groundwater flow and chemical and isotopic composition at a demonstration site for carbon dioxide storage in a depleted natural gas reservoir

Between March 2008 and August 2009, 65,445 tonnes of ∼75 mol% CO₂ gas were injected in a depleted natural gas reservoir approximately 2000 m below surface at the Otway project site in Victoria, Australia. Groundwater flow and composition were monitored biannually in two overlying aquifers between June 2006 and March 2011, spanning the pre-, syn- and post-injection periods. The shallower (∼0–100 m), unconfined, porous and karstic aquifer of the Port Campbell Limestone and the deeper (∼600–900 m), confined and porous aquifer of the Dilwyn Formation contain valuable fresh to brackish water resources. Groundwater levels in either aquifer have not been affected by the drilling, pumping and injection activities that were taking place, or by the rainfall increase during the project. In terms of groundwater composition, the Port Campbell Limestone groundwater is brackish (electrical conductivity = 801–3900 μS cm⁻¹), cool (temperature = 12.9–22.5 °C), and near-neutral (pH = 6.62–7.45), whilst the Dilwyn Aquifer groundwater is fresher (electrical conductivity = 505–1473 μS cm⁻¹), warmer (temperature = 42.5–48.5 °C), and more alkaline (pH = 7.43–9.35). Carbonate dissolution, evapotranspiration and cation exchange control the composition of the groundwaters. Comparing the chemical and isotopic composition of the groundwaters collected before, during and after injection shows no statistically significant changes; even if they were statistically significant, they are mostly not consistent with those expected if CO₂ addition had taken place. The monitoring program reveals no impact on the groundwater resources attributable to the C storage demonstration project.