Deciphering the interaction between quaternary and continental Sabkhas aquifers in Central Tunisia using hydrochemical and isotopic tools

Climate aridity and intensive exploitation due to uncontrolled pumping for irrigation have caused a drastic decrease in the piezometric level of the shallow aquifer of Chougafiya plain, central Tunisia, and have seriously degraded groundwater quality. According to the hydrochemical data (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Br^?, Na⁺, Mg²⁺, K⁺, Ca²⁺, Sr²⁺) and the stable isotopes (¹⁸O and ²H content), groundwater salinization in the investigated aquifer is caused by four main processes: (1) evaporite dissolution (2) cation exchange reactions (3) evaporation processes and (4) mixing with Sabkhas salt water causing salinity to increase in the central and southern parts of the basin. The radiogenic (³H) isotope data provided insight into the presence of significant contemporaneous recharge waters in the western part of the shallow aquifer. The movement of the tritiated water may have occurred according to the general flow path (NW–SE). When tritium was used in conjunction with the stable isotopes and chloride, the mixing process could be clearly identified, especially in the central part of the study area.     

B and Li isotopes as intrinsic tracers for injection tests in aquifer storage and recovery systems

Boron and Li isotopes have been tested as environmental tracers of treated sewage injected into a sandy aquifer (Shafdan reclamation project, Israel). During a 38 days injection test in a newly dug injection well, a conservative artificial tracer (Br⁻) was monitored together with δ¹¹B and δ⁷Li in the injectate, in the unsaturated soil zone (porous cup) and an observation well in the aquifer. In spite of B and Li concentrations in the injectate close to background values, significant shifts of the isotope signatures could be observed over the duration of the injection test. Boron isotope ratios show a breakthrough curve delayed with respect to Br⁻ breakthrough due to some reversible sorption on the aquifer material. No isotope fractionation was observed in the unsaturated or the saturated zone so that B isotopes can be considered as conservative in the investigated part of the aquifer system. Lithium isotopes are strongly fractionated, probably due to sorption processes. Lithium concentrations point to a Li sink in the system, δ⁷Li values vary strongly with a tendency of ⁷Li depletion in the liquid phase over the duration of the experiment. This is opposite to the expected preferential sorption of ⁶Li onto clay minerals. Boron isotopes reveals a valuable tracer of artificial recharge of freshwaters derived from treated sewage, both for short term tracer tests and for long-term monitoring of artificial recharge, even if in aquifers with higher clay contents, sorption-linked isotope fractionation cannot be excluded. More data are needed on Li isotope fractionation in natural groundwater systems to assess the potential of this tracer as monitoring tool.     

Gd-DTPA in the hydrosphere: Kinetics of transmetallation by ions of rare earth elements,Y and Cu

The kinetics of transmetallation of Gd³⁺ in diethylenetriaminpentaacetic acid (Gd-DTPA) by rare earth elements (except Yb), Y³⁺ and Cu²⁺ has been studied in test solutions ranging from pH 5 to 6.5 in order to understand the distribution and longevity of their chelates in the hydrosphere. Chelated and non-chelated species were separated by adsorption of the free ions by clay minerals before analysis by ICP-MS. This simple method allows determining the distribution of DTPA chelates at concentration levels as low as a few 10 pmol/l. The transmetallation constants at ionic strength of 0.01 mol/l and room temperature are commensurable with those derived from published formation constants of the corresponding DTPA complexes. It could be proved that DTPA chelates of rare earth elements, Y and Cu are stable at least over 6 months. The pattern of the second-order rate constants shows a strong tetrad effect, which is not displayed by the pattern of transmetallation constants. Based on these results, the rate of transmetallation of Gd-DTPA under natural conditions is derived. The resultant process yields 10% turn-over of initial Gd-DTPA within two months, if Cu²⁺ concentrations are below 1 nmol/l. At higher concentrations, the turn-over increases with elapsed time. Equilibrium among REE and Y is expected only after tens of years. This makes Gd-DTPA a powerful tracer in hydrological studies.     

Behavior of Gd-DTPA in simulated bank filtration

The behavior of Gd-DTPA during bank filtration was simulated in a 30 m column filled with Pleistocene sand and flushed by surface water from a lakeside in Berlin, Germany. The surface water is about a 1:1 mixture of river water and effluents from a sewage treatment plant. Throughout 34 days this water was continuously spiked with Gd-DTPA at a level of 60 μg/L. The broad plateau of the Gd-DTPA pulse declined by 15.4% within 34 days by transmetallation. Nine percentage of the total decline is caused by Y and rare earth elements; the remaining part is attributed to Cu²⁺ which is the most influential metal in surface water. All other metals also contributing to transmetallation are combined with Cu to Cu equivalents because only the rate constant of transmetallation of Cu²⁺ is known. The analytical results of the column effluents prove the pseudo-first-order kinetics of transmetallation based on reversible sorption of metals by pools in the column sediment and disprove biodegradation at noticeable levels. The mass ratio of water to tracer is <10¹⁰.     

Hydrochemical and isotopic characterisation of the Bathonian and Bajocian coastal aquifer of the Caen area (northern France)

This paper describes the geochemical evolution of groundwater in the Bathonian and Bajocian aquifer along its flowpath. Since this aquifer represents one of the main sources of fresh water supply in the Caen area and has been subjected to a Holocene marine intrusion, its management requires a sound knowledge of (1) the primary conditions and (2) the potential influence of either natural or anthropogenic pressures. Groundwater vertical sampling validity is discussed with the contribution of high resolution temperature logging. The main processes of geochemical evolution along a groundwater flow line and the sea-water intrusion characteristics are discussed using ionic concentrations (Br⁻, F⁻ and major elements) and isotopes (water δ²H and δ¹⁸O, TDIC δ¹³C and A¹⁴C, sulphate δ¹⁸O and δ³⁴S). As the ¹³C content of TDIC is used as a tracer of water-rock interaction, it shows evidence of specific chemical and isotopic evolutions of groundwater within the aquifer, both related to water-rock interaction and mineral equilibria in groundwater. All the above-mentioned tracers evolve downflow: cation concentrations are modified by exchange with clay minerals allowing a high F⁻ concentration in groundwater, whereas Br⁻ and SO²⁻₄ concentrations appear to be redox condition dependant. Superimposed on these geochemical patterns, δ¹⁸O and δ²H compositions indicate that aquifer recharge has varied significantly through time. The chemical evolution of groundwater is locally affected by a salty water intrusion that is characterised by mixing between Flandrian fresh water and sea-water which has interacted with peat as evidenced by a high Br⁻/Cl⁻ ratio and SO²⁻₄ reduction.     

Assessment of an arid region soil capacity on natural attenuation of municipal treated wastewater: a column experiment using soil of Varamin area,Iran

Soil aquifer treatment (SAT) is an effective indirect technique for wastewater reuse. The present study aims at assessing the soil capacity in arid region of Varamin on natural attenuation of inorganic constituents of municipal treated wastewater of Tehran City. In order to simulate SAT pond, four columns of 30 cm in height and 4 cm in diameter were filled with sandy loam soil taken from artificial recharge pond in Varamin plain. These columns were recharged by secondary treated wastewater from Shahre-Rey treatment plant under the plan of 12-h wetting and drying cycles. During the experiment, 50 pore volume passed through each column. The pH, EC, TDS, SAL, SAR, major ions, nitrate, phosphate and trace elements were measured in influent and effluent samples. The concentration of Na⁺, Ca²⁺, Mg²⁺, Cl^? and SO₄^2? increased in effluent samples due to a washout process and dissolution of minerals. The soil could only attenuate NO₃^?, K⁺, Rb and PO₄^3? with the percentage of 18.4, 24.6, 67.7 and 83.6, respectively. The soil of studied area is rich in Cr, Ni, Sr, Pb, Cu, Zn, Ba and Rb. The concentrations of all mentioned trace elements, with the exception of Rb, have increased in the effluent samples with respect to influent. Also, the quality indices of TDS, SAL and SAR have increased 10.6, 25.2 and 8.7%, respectively, in effluent. Soil column samples, at the end of experiment, contain high amounts of major and trace elements. Consequently, there is a potential risk for groundwater contamination in long-term recharge.     

Impact of anthropogenic activities on the chemistry and quality of groundwater: a case study from a terrain near Zarand City, Kerman Province, SE Iran

Groundwater of an aquifer located in the vicinity of a large coal washery near Zarand City, Iran consists of two hydrochemically differing facies, which have been informally designated as groundwater (A) and groundwater (B). Groundwater (A) is native, brackish in composition and is characterized by Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and SO₄ ^2? > HCO₃ ^? > Cl^? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, and values of chloro-alkaline indices, C ratio and Na⁺/Cl^? molar ratio indicate that in the groundwater (A), the ionic load of Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ^2? and HCO₃ ^? is derived essentially from weathering of both carbonates and aluminosilicates and direct cation and reverse cation–anion exchange reactions. Groundwater (B) is the polluted variant of the groundwater (A), brackish to saline in composition, and unlike the groundwater (A), consists of HCO₃ ^? as the dominant anion. In comparison with the groundwater (A), the groundwater (B) contains higher concentrations of all ions, and its average ionic load (av. = 59.74 me/L) is 1.43 times higher than that of the groundwater (A) (av. = 41.54 me/L). Additional concentrations of Ca²⁺, Mg²⁺, K⁺, SO₄ ^2?, Cl^? and HCO₃ ^? in the groundwater (B) are provided mainly by downward infiltrating water from the coal washery tailings pond and reverse cation–anion exchange reaction between tailings pond water and exchanger of the aquifer matrix during non-conservative mixing process of groundwater (A) and tailings pond water. Certain additional concentrations of Na⁺, K⁺ and NO₃ ^? in the groundwater (B) are provided by other anthropogenic sources. Quality wise, both groundwaters are marginally suitable for cultivation of salt-tolerant crops only.     

Field tracer test for denitrification in a pyrite-bearing schist aquifer

A small-scale artificial tracer test performed on a schist aquifer in Brittany has helped clarify mechanisms and kinetics of in situ autotrophic denitrification. NO₃ was injected as a pulse simultaneously with a conservative tracer -Br⁻. During the test, which lasted 210 h, 73% of the injected Br⁻ was recovered, as against only 47% of the NO₃. The 26% difference in the recovery of the two injected species is interpreted as being the result of denitrification, in part due to the direct oxidation of pyrite present in the solid aquifer according to the reaction: 5FeS₂+14NO₃⁻+4H⁺→7N₂+10SO₄²⁻+5Fe²⁺+2H₂O, and in part due to subsequent iron oxidation according to the reaction: NO₃⁻+5Fe²⁺+6H⁺→1/2N₂+5Fe³⁺+3H₂O. Despite the potential increase in SO₄ and Fe resulting from denitrification through pyrite oxidation, the concentrations of these elements in the groundwater remain moderate due to the precipitation of minerals such as jarosite and/or natroalunite. Tracer transfer takes place in a heterogeneous medium which, according to the breakthrough curves, can be simplified to a dual-porosity aquifer comprising a high-permeability (fractures or large fissures) medium of low porosity from which only minor denitrification of circulating NO₃-bearing water was observed and a low-permeability (small fissures) medium of high porosity which induces a higher denitrification rate in the circulating NO₃-bearing water. The kinetics of the denitrification reaction are high compared with results obtained for other environments and can be described by a first-order model with a half life of 7.9 days for the low-porosity medium and only 2.1 days for the high-porosity medium.     

Hydrochemical evolution of groundwater in a riparian zone affected by acid mine drainage (AMD), South China: the role of river–groundwater interactions and groundwater residence time

Investigations were undertaken in the riparian zone near Shangba village, an AMD area, in southern China to determine the effects that river–groundwater interactions and groundwater residence time have had on environmental quality and geochemical evolution of groundwater. Based on the Darcy’s law and ionic mass balances as well as the method of isotopic tracer, the results showed that there were active interactions between AMD-contaminated river water and groundwater in the riparian zone in the study area. River water was found to be the main source of groundwater recharge in the northwestern part of the study area, whereas groundwater was found to be discharging into the river in the southeastern part of the study area throughout the year. End-member mixing analysis quantified that the contributions of river water to groundwater decreased gradually from 35.9% to negligible levels along the flow path. The calculated mixing concentrations of major ions indicated that water–rock reactions were the most important influence on groundwater quality. The wide range of Ca²⁺?+?Mg²⁺ and HCO₃^? ratios and the change of groundwater type from Ca²⁺–SO₄^2? type to a chemical composition dominated by Ca²⁺–HCO₃^? type indicated a change of the major water–rock reaction process from the influence of H₂SO₄ (AMD) to that of CO₂ (soil respiration) along a groundwater flow path. Furthermore, the kinetics interpretation of SO₄^2? and HCO₃^? concentrations suggested that the overlapping time of their kinetics triggered the hydrochemical evolution and the change of major weathering agent. This process might take approximately 8 years and this kinetic time will be continued when a steady source of contamination enter the aquifer.     

Groundwater chemical and fecal contamination assessment of the Jerba unconfined aquifer,southeast of Tunisia

Located in the southeast of Tunisia, on the Mediterranean Sea, Jerba Island has a semiarid climate condition. The surface water scarcity has made groundwater the main source to supply the domestic, touristic, and agricultural water demand. Unconfined aquifer is a vulnerable costal aquifer system that undergoes several phenomena. This work aims at assessing the geochemical and bacteriological groundwater quality, defining groundwater pollution sources and promoting sustainable development and effective management of groundwater resources in Jerba Island. Data were collected after the wet season in 2014 from 79 wells. Electric conductivity, pH, TDS, and major and fecal tracers (total coliforms, thermotolerant coliforms, Escherichia coli, and Salmonella) were analyzed. Geochemical modeling including the relationships between geochemical tracers Na⁺ vs. Cl^?, Ca²⁺ vs. Cl^?, K⁺ vs. Cl^?, representative ionic ratios (Br^?/Cl^?, Na⁺/Cl^?, Mg²⁺/Ca²⁺), and statistical analysis were used to specify major process contributing to groundwater pollution and main factors controlling groundwater mineralization in the island. Groundwater varieties were hydrochemically classified into three types in terms of salinity values: group 1 (8.86%) to fresh water, group 2 (27.84%) to brackish water, and group 3 (63.29%) belongs to saline water. In addition, groundwater quality revealed high concentrations in chemical pollution tracers (Na⁺, Cl^?, SO₄ ^2?, and NO₃ ^?) and fecal tracers. Besides, most of the sampled wells were contaminated with nitrate (50.63%). Also, thermotolerant coliforms and E. coli were detected in all groundwater samples (96.2% of wells). Results indicated that the Jerba shallow aquifer was under serious threat from both natural and anthropogenic contamination. However, the wild discharge of domestic effluents, septic tanks, and sewage were the main origins of underground water contamination in Jerba Island. The reduction of fecal sources, through constructing normalized latrines is thus recommended.     

Deep reaching fluid flow in the North East German Basin: origin and processes of groundwater salinisation

Major element chemistry, rare-earth element distribution, and H and O isotopes are conjointly used to study the sources of salinisation and interaquifer flow of saline groundwater in the North East German Basin. Chemical analyses from hydrocarbon exploration campaigns showed evidence of the existence of two different groups of brines: halite and halite Ca–Cl brines. Residual brines and leachates are identified by Br^?/Cl^? ratios. Most of the brines are dissolution brines of Permian evaporites. New analyses show that the pattern of rare-earth elements and yttrium (REY) are closely linked to H and O isotope distribution. Thermal brines from deep wells and artesian wells indicate isotopically evaporated brines, which chemically interacted with their aquifer environment. Isotopes and rare-earth element patterns prove that cross flow exists, especially in the post-Rupelian aquifer. However, even at depths exceeding 2,000 m, interaquifer flow takes place. The rare-earth element pattern and H and O isotopes identify locally ascending brines. A large-scale lateral groundwater flow has to be assumed because all pre-Rupelian aquifer systems to a depth of at least 500 m are isotopically characterised by Recent or Pleistocene recharge conditions.     

Estimation of contaminant transport parameters for a tropical sand in a sand tank model

This research describes the goals, design and implementation of a quasi natural gradient, laboratory scale, sand tank (aquifer) model experiment. The model was used to study the transport of an inorganic tracer (Chloride) in groundwater, within a tropical aquifer (porous medium) material. Three-dimensional sand tank (1.8 m × 0.3 m × 0.8 m) experiments were conducted to investigate contaminant transport and natural attenuation within the sand tank. In all, 360 samples were collected during 24 sampling sessions, for the three days of the tracer experiments in the Sand Tank. The Owena sand is a poorly graded sand with 88.1 % sand and 11.9 % gravel. Geotechnical properties including; coefficient of uniformity C_u = 2.53, coefficient of gradation C_z = 0.181, hydraulic conductivity K = 5.76 × 10^?4 m/s, bulk density p = 1.9 Mg/m³, effective porosity n_e = 0.215 and median grain diameter D₅₀ = 0.55 mm, were determined. Other relevant hydraulic and solute transport parameters, such as dispersion coefficients and dispersivities were also established for the tropical soil.     

Effective porosity and specific yield of a sedimentary rock determined by a field tracing test using tritium as a tracer

Effective porosity value was analyzed from the tritium concentration of sampled groundwater using a three-dimensional groundwater-flow and advection-dispersion code based on the finite element method. The effective porosity value was about 10%. Porosity values measured from core samples were 7–15%. The groundwater flow velocity estimated from the tritium concentrations was about 1 × 10^–5 cm s^–1. Therefore, during the low groundwater flow velocity condition, effective porosity and porosity values were the same. At the same test site, a 0.48% effective porosity value, determined by another tracer test injecting Br^– solution into the aquifer during groundwater level change, was smaller than the porosity value when the flow velocity was 1.8×10^–2 cm s^–1. Thus the effective porosity value is concluded to be due to groundwater flow velocity. The specific yield value was calculated to be 0.6% by the total volume of tunnel seepage water and the total volume of the rock unsaturated during tunnel construction. However, as pore water continued to be drained after the groundwater level change was completed, the specific yield value became larger than 0.6%. Thus specific yield value is concluded to be due to drainage time.     

Chemical characterization of the Neogene Aquifer, Belgium

The evolution of groundwater chemistry along the direction of groundwater flow was studied using hydrochemical data from samples collected along a flow line in the Neogene Aquifer, Belgium. Infiltrating water was found to have a very low mineral content and low pH because the sediments are strongly decalcified. Increasing SiO₂ and cation concentrations along the groundwater flow line indicate silicate-weathering processes, confirmed with the aid of saturation indices, calculated with PHREEQC, and stability diagrams. A classification system based on redox sensitive species was developed and shows that an extensive redox sequence is present in the aquifer. At a shallow depth, pyrite oxidation has caused an increase in sulphate, while iron is precipitated as hydroxides. Elevated arsenic concentrations are related to the reduction of these iron hydroxides at a relatively shallow depth and to the dissolution of siderite at greater depth. Dissolution of carbonate in the aquifer material, present in deep layers and to the north, has lead to increased Ca²⁺ and HCO₃ ^? concentrations. The Ca²⁺ from the groundwater is exchanged for Na⁺, Mg²⁺ and K⁺ adsorbed to the clay surfaces at the bottom of the groundwater reservoir. Although the Neogene Aquifer is well flushed, there are still some marine influences present in the deepest parts.     

Origin and distribution of saline groundwaters in the upper Miocene aquifer system, coastal Rhodope area, northeastern Greece

 This paper describes the origins and distribution of saline groundwaters in the coastal area of Rhodope, Greece. The aquifer system includes two aquifers within coarse-grained alluvial sediments in the coastal part of the study area. Two major water-quality groups occur in the study area, namely Ca²⁺-rich saline groundwater and Ca²⁺-poor, almost fresh groundwater. The main process controlling the groundwater chemistry is the exchange of calcium and sodium between the aquifer matrix and intruding seawater. The natural salt water in the study area is probably residual water that infiltrated the aquifer system during repeated marine transgressions in late Pleistocene time. Seawater intrusion into the coastal aquifer system occurs as a result of overpumping in two seawater wedges separated vertically by a low-permeability layer. The rate of intrusion averages 0.8 m/d and is less than expected due to a decline of the aquifer's permeability at the interface with the seawater. The application of several hydrochemical techniques (Piper and Durov diagrams; Na⁺/Cl^–, Ca²⁺/Cl^–, Mg²⁺/Cl^–, and Br^–/Cl^– molar ratios; Ca²⁺/Mg²⁺ weight ratio; and chloride concentrations), combined with field observations, may lead to a better explanation of the origin of the saline groundwater. Received, May 1997 / Revised, May 1998, December 1998 / Accepted, February 1999     

Quantifying stream-loss recovery in a spring using dual-tracer injections in the Snake Creek drainage,Great Basin National Park,Nevada, USA

Simultaneous short-pulse injections of two tracers (sodium bromide [Br^–] and fluorescein dye) were made in a losing reach of Snake Creek in Great Basin National Park, Nevada, USA, to evaluate the quantity of stream loss through permeable carbonates that resurfaces at a spring approximately 10 km down drainage. A revised hydrogeologic cross section for a possible flow path of the infiltrated Snake Creek water is presented, and the results may inform water management in the region. First arrival and peak concentration of the two tracers occurred at 9.5 and 12.7 days after injection, respectively. Fracture transport simulations indicate that Br^– preferentially diffuses into immobile regions of the aquifer, and this diffusive flux is likely responsible for the major differences in the breakthrough curves. When considering the diffusive tracer flux, total apparent Br^– and fluorescein dye recoveries were 16.9–22.1% and 21.7–24.3%, respectively. These findings imply that consideration of diffusive flux and long-term monitoring in fracture-dominated flow may support accurate quantification of tracer recovery. In addition, the apparent power law slopes of the breakthrough tails for both tracers were steeper at early times than have been attributed to heterogeneous advection or channeling in meter-scale tests, but the late-time Br^– power law slope becomes less steep than has been attributed to diffusive exchange. These deviations may reflect fracture transport patterns that occur at larger scales.

     

Groundwater salinization processes in shallow coastal aquifer of Djeffara plain of Medenine, Southeastern Tunisia

Urban and industrial development and the expansion of irrigated agriculture have led to a drastic increase in the exploitation of groundwater resources. The over-exploitation of coastal aquifers has caused a seawater intrusion and has seriously degraded groundwater quality. The shallow coastal aquifer of the Djeffara plain, southeastern Tunisia constitutes an example of water resource suffering an intensive and uncontrolled pumping for irrigation. Intensive exploitation of the aquifer and climate aridity caused a decrease in piezometric level and an increase in salinity. According to the hydrochemical data (Cl⁻, SO₄ ²⁻, NO₃ ⁻, HCO₃ ⁻, Br⁻, Ca²⁺, Mg²⁺, Na⁺, K⁺) and the stable isotope composition (oxygen-18 and deuterium content), groundwater salinization in the investigated system is caused by three main processes: (i) salts dissolution especially in the central part of Jerba and around Medenine plain; (ii) evaporation process; and (iii) seawater intrusion which caused the increase in salinity in the peninsula of El Jorf, in Jerba and in the North of Ben Gardane.     

In situ push-pull tests for the determination of TCE degradation and permanganate consumption rates

A simple, single-well push-pull test was conducted at a TCE-contaminated site to estimate the site-specific TCE degradation and permanganate (MnO₄⁻) consumption rate. Known quantities of a conservative tracer (Br⁻) and permanganate were rapidly injected into a saturated aquifer then periodically sampled during extraction from the same well. Concentrations of Br⁻, TCE, and MnO₄⁻ were measured; breakthrough curves (BTCs) for all species of solute were determined. Data analysis of BTCs for bromide and TCE showed that the first-order rate constant of TCE degradation by MnO₄⁻ is 1.67 ± 0.152 h⁻¹. Further, the in situ MnO₄⁻ demand rate by TCE and aquifer materials is estimated to be 0.54 ± 0.371 h⁻¹. This study demonstrates that in situ push-pull tests are useful and economical tools for field investigations to determine contaminant reaction and oxidant consumption rates, which may then be used to optimize groundwater remediation designs.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Influence of upwelling Zechstein sulphate on the concentration and isotope signature of sedimentary sulphides in a fluvioglacial sand aquifer

Very low concentrations of total S, mainly sedimentary sulphides, were quantitatively extracted from Quaternary sands of the Elbe Basin, using HNO₃, Br₂ and HCl, to distinguish 3 aquifer zones:

• •an upper aerobic section, containing low concentrations (only a few ppm) of non-sulphidic S compounds,
• •the central and lower part of the aquifer, dominated by ³⁴S-depleted sedimentary Fe sulphides, formed by reduction of infiltrating SO₄, derived from groundwater recharge, and
• •the lowest 5–10 m of the aquifer, containing high concentrations of ³⁴S-enriched sulphides.

The latter originated from dissolved Zechstein SO₄, which was reduced during upwelling through the organic-rich Tertiary aquiclude. H₂S and HS⁻ reacted and precipitated with Fe and other metal ions shortly after migration into the C_org-poor Quaternary aquifer. The sulphides yield valuable information concerning the ascent of confined saline solutions from isolated Zechstein evaporites inside the “Mühlberger Graben”, which is covered by Cenozoic sediments and whose extension and boundaries are therefore not well defined. Only a few locations, close to faults and geological windows, show deep-water admixture sufficiently strong to cause visible changes in hydrochemistry and isotopic ratios of SO₄ and DIC directly above the base of the Quaternary. Sulphides showing different origins may possibly be used in other areas to provide information concerning underlying geology and hydrodynamics.