Geochemical and isotopic characterization of groundwater from the Paleogene limestone aquifer of the Upper Jezireh,Syria

This research aims to evaluate the groundwater resources of Paleogene aquifer in the Upper Jazireh area (Syria), in terms of chemical water type, recharge zones and water ages. The results show that the main recharge zones for the Paleogene aquifer range between 650 and 900 m a.s.l., which coincide with the outcrop of the karstified limestone in the Mardin uplift. The chemical and isotopic behaviors of groundwater, together with radiometric ¹⁴C reflect the existence of three different groundwater groups: (1) the fresh and cold water, percolating in short and shallow flow paths, for which the main replenishment processes are recent; (2) the brackish and thermal water containing certain amounts of H₂S gas, that percolate in longer and deeper flow paths, for which the main replenishment processes occurred during the palaeoclimatic humid conditions of Pleistocene time, placed at 10–18 Ka BP; (3) the brackish and admixed thermal groundwater with intermediate ¹⁴C age, which seems to be formed as a result of mixing between the previous two groups.     

Geochemical characteristics of shallow groundwater in Datong basin, northwestern China

Located in semi-arid regions of northwestern China, Datong basin is a Quaternary sedimentary basin, where groundwater is the most important source for water supply. It is very important to study groundwater characteristics and hydrogeochemical processes for better management of the groundwater resource. We have identified five geochemical zones of shallow groundwater (between 5 and 80 m) at Datong: A. Leaching Zone (Zone I); B. Converging Zone (Zone II); C. Enriching Zone (Zone III); D. Reducing Zone (Zone IV); E. Oxidizing Zone (Zone V). In Zones I, II, and V and some parts of Zones III and IV, hydrolysis of albite/K-feldspar/chalcedony system and/or albite/K-feldspar/quartz system enhanced concentrations of Na⁺, K⁺, HCO₃⁻ and silicate. In Zone I, dissolution of carbonate and hydrolysis of feldspar generally controlled the groundwater chemistry. Infiltration of meteoric water promoted the formation of HCO₃⁻ in the water. In Zone II, the main geochemical processes influencing the groundwater chemistry were dissolutions of calcite and dolomite, ion exchange and evaporation. In Zones III and IV, in addition to ion exchange, evaporation and precipitation of calcite and dolomite, leaching of NaHCO₃ in saline–alkaline soils dominated the water quality. Zone IV was under anoxic condition, and reduction reactions led to the decrease of SO₄²⁻, NO₃⁻ and occurrence of H₂S, with the highest arsenic content (mean value of 366 μg/L), far exceeding Maximum Contaminant Level (MCL). Abnormal arsenic in the groundwater resulted in endemic disease of waterborne arsenic poisoning among local people. Zone V overlapped Zone I was intensively affected by coal mining activities. Sulfide minerals, such as pyrite, would have been oxidized when exposed to air due to coal mining, which directly added sulfate to groundwater and thus increased SO₄²⁻ concentration. Oxidization of sulfide minerals also decreased pH and promoted dissolutions of calcite and dolomite.     

Geochemical characterization of source rock from the north bank area,upper Assam basin

The study area is confined to a part of upper Assam basin, north of river Brahmaputra (north bank). Seven exploratory wells have been drilled in this part of the basin in order to probe the hydrocarbon prospects of the area. The exploratory efforts did not indicate significant hydrocarbon prospects in the north bank. Since the presence of source rock is an important component of the petroleum system, a detailed systematic study of source rock potential was carried out by analysing known source rock intervals in these seven wells. In the present study, Rock-Eval pyrolysis combined with specific geochemical analyses like GC and TLCFID has been used to characterise the source rocks, their distribution and thermal maturity of the organic matter. The source rocks in the area show mainly Type III, land-plant derived organic matter along with some Type II organic matter. They are predominantly gas prone in nature, although mixed and oil-prone source rocks are occasionally present. Although source rock intervals have been identified in the Langpar, Sylhet limestone and Kopili formations, the Barail Group and the Tipam sandstone Formation, the bulk of the source rock occurs within the Kopili Formation. Geochemical analyses of the cores indicate oil signatures at certain depths, although no commercial oil was discovered. The hydrocarbon generation potential of these source rocks are constrained by low maturity at the presently drilled depths.     

Geochemical characterization of groundwater from shallow aquifer surrounding Fetzara Lake N. E. Algeria

Hydrogeochemical investigations were carried out around Fetzara Lake, Northeast Algeria, to assess the quality of groundwater for its suitability for drinking and irrigation purposes. The groundwater chemistry is mainly controlled by the water?Crock interactions, but also influenced by other processes such as evapotranspiration and ion exchange. Groundwater samples collected, during two periods (1993 and 2007) from wells in the area were analyzed for pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, CO ₃ ^2? , HCO ₃ ^? , Cl^?, SO ₄ ^2? , and NO ₃ ^? . The chemical relationships in Piper??s diagram and Gibbs??s diagram suggest that groundwaters mainly belong to noncarbonate alkali type and Cl^? group and are controlled by evaporation dominance, respectively, due to the sluggish drainage conditions, greater water?Crock interaction, and anthropogenic activities. A comparison of the groundwater quality in relation to drinking water quality standards proves that most of the water samples are not suitable for drinking. US Salinity Laboratory??s and Wilcox??s diagrams and %Na⁺ used for evaluating the water quality for irrigation suggest that the majority of the groundwater samples are not good for irrigation.     

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.     

The deep Cretaceous aquifer in the Aleppo and Steppe basins of Syria: assessment of the meteoric origin and geographic source of the groundwater

A drilling project was carried out in Syria to assess the potential of the deep groundwater resources of the Cretaceous aquifer, composed of Cenomanian-Turonian limestones and dolomites. In this context, isotope (¹⁴C, ³H, δ¹³C, δ¹⁸O, δ²H) and hydrochemical analyses were performed on wells in and around the Aleppo and Steppe basins. The interpretation includes complementary results from published and unpublished literature. The results provide evidence that many new wells pump mixed groundwater from the Cretaceous aquifer and the overlying Paleogene aquifer. Radiocarbon measurements confirmed dominating Pleistocene groundwater in the Cretaceous aquifer and mainly Holocene groundwater in the Paleogene aquifer. Most groundwater in the Cretaceous aquifer seems to be recharged in the western limestone ridges, stretching from Jebel az Zawiyah (south of Idlep) via Jebel Samane (south of Afrin and A’zaz) to the region north of Aleppo, and in the Northern Palmyrides mountain belt. Some recharge also occurs around the basalt plateau of the Jebel al Hass, south east of Aleppo. It is concluded that the Taurus Mountains and the Euphrates River do not recharge the Cretaceous aquifer. The sources of recharge seem to be occasionally occurring intensive winter storms that approach from Siberia.     

Interaction between shallow and deep aquifers in the Tivoli Plain (Central Italy) enhanced by groundwater extraction: A multi-isotope approach and geochemical modeling

In the Tivoli Plain (Rome, Central Italy) the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using isotopic and chemical tracers. A conceptual model of the groundwater flowpaths has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as DIC/Cl⁻, Ca/(Ca + Mg)/SO₄/(SO₄ + HCO₃), and environmental isotopes (δ¹⁸O, δ²H, ⁸⁷Sr/⁸⁶Sr, δ³⁴S and δ¹³C) was carried out in order to determine the sources of recharge of the aquifer, the origin of solutes and the mixing processes in groundwater of Tivoli Plain. Multivariate statistical methods such as principal component analysis and Cluster analyses have confirmed the existence of different geochemical facies and the role of mixing in the chemical composition of the groundwater.     

Hydrogeochemical evolution of the shallow and deep basaltic aquifers in Tamborine Mountain,Queensland (Australia)

Tamborine Mountain, Queensland (Australia), is a prime example of a basalt fractured-rock aquifer. Yet very little is known about the hydrochemistry of this groundwater system. Both analytical (major ions and stable isotopes) and multivariate (hierarchical cluster analysis, principal component analysis and factor analysis) analyses were used in this study to investigate the factors that interact within this aquifer system, in order to determine groundwater hydrogeochemistry. A new approach was applied to the data by classifying hydrographs by water type to clearly identify differing aquifer zones. Three distinct groundwater chemistry types were identified, and they were differentiated by variations in depth. Shallow bores were dominated by Na–Cl waters, deep bores were dominated by Na–HCO₃ and Ca–HCO₃ waters, and the two deepest bores were dominated by mixed water types. The evaluation of hydrogeochemical data has determined that both mineral weathering processes and groundwater/surface-water interaction had a strong influence on the hydrogeochemistry. Seasonal effects were minimal in the study area based on physicochemical parameters and ion chemistry. However, stable isotopic data show temporal trends. Increased rainfall events during the wet season produced a depletion in δ¹⁸O and increased d-excess values. The opposite is found during the dry season as a result of higher evaporation rates that are not hindered by intense rainfall events.

     

Isotope hydrology of deep groundwater in Syria: renewable and non-renewable groundwater and paleoclimate impact

The Regional Deep Cretaceous Aquifer (RDCA) is the principal groundwater resource in Syria. Isotope and hydrochemical data have been used to evaluate the geographic zones in terms of renewable and non-renewable groundwater and the inter-relation between current and past recharge. The chemical and isotopic character of groundwater together with radiometric ¹⁴C data reflect the existence of three different groundwater groups: (1) renewable groundwater, in RDCA outcropping areas, in western Syria along the Coastal and Anti-Lebanon mountains. The mean δ¹⁸O value (?7.2 ‰) is similar to modern precipitation with higher ¹⁴C values (up to 60–80 pmc), implying younger groundwater (recent recharge); (2) semi-renewable groundwater, which is located in the unconfined section of the RDCA and parallel to the first zone. The mean δ¹⁸O value (?7.0 ‰) is also similar to modern precipitation with a ¹⁴C range of 15–45 pmc; (3) non-renewable groundwater found in most of the Syrian interior, where the RDCA becomes confined. A considerable depletion in δ¹⁸O (?8.0 ‰) relative to the modern rainfall and low values of ¹⁴C (<15 pmc) suggest that the large masses of deep groundwater are non-renewable and related to an older recharge period. The wide scatter of all data points around the two meteoric lines in the δ¹⁸O-δ²H diagram indicates considerable variation in recharge conditions. There is limited renewable groundwater in the mountain area, and most of the stored deep groundwater in the RDCA is non-renewable, with corrected ¹⁴C ages varying between 10 and 35 Kyr BP.     

Hydrogeological and thermal characterization of shallow aquifers in the plain sector of Piemonte region (NW Italy): implications for groundwater heat pumps diffusion

The low annual and seasonal variability of the shallow groundwater temperature in the alluvial plain aquifers of the Piemonte region (NW Italy) confirmed the potentiality of the low-enthalpy open-loop groundwater heat pumps (GWHP) diffusion to contribute to the reduction of regional greenhouse gas emissions. The distribution of mean groundwater temperatures ranged from a minimum of 10.3°C to a maximum of 17.9°C with a mean of 14.0°C. Differences among diverse areas were slight according with the modest variations in the general climatic condition. Like the air, temperature distribution of the shallow groundwater temperatures is generally similar to topographic elevations in reverse manner. Higher temperature values recorded were typical of summer months (June, July). On the opposite lower values were measured in January and February. No significant difference phase (time) difference between air and groundwater temperature appeared in the data analysis. Besides air-temperature influence (seasonal variability) seemed strictly connected to the depth to groundwater in the measure point and it was negligible when the value was over 9.5 m. For the application of the open-loop systems, extensive examinations of the hydrogeological local conditions should be conducted at site scale and groundwater heat transport modelling should be developed.     

Geochemical characterization of groundwater from an arid region in India

A study on the geochemical processes in arid region of western India (Kachchh district) was carried out using major, minor, trace metal data and isotopic composition (δ²H, δ¹⁸O) of groundwaters. Results indicate that the distribution of chemical species in groundwater of this district is controlled by leaching of marine sediments, dissolution of salts in root zone and incongruent dissolution of carbonate minerals. Common inorganic contaminants such as fluoride, nitrate and phosphate are within drinking water permissible limits. However, most of the samples analyzed contain total dissolved salts more than desirable limits and fall in doubtful to unsuitable category with regard to irrigational purpose. Trace metal data indicates no contamination from toxic elements such as arsenic and lead. An increased salt content is observed in groundwater at shallower depths indicating mixing with surface water sources. The chemical characteristics of the groundwater have found to be strongly dependent on the local lithological composition. Environmental isotopic data indicates that the groundwater is of meteoric origin and has undergone limited modification before its recharge. The processes responsible for observed brackishness are identified using chemical and isotope indicators, which are in agreement with subsurface lithology and hydrochemistry. These data though represent hydrochemical scenario of 2001 can still be used for understanding the long-term fluctuations in water chemistry and would be quite useful for the planners in validating groundwater quality models.     

The origin and isotopic composition of dissolved sulfide in groundwater from carbonate aquifers in Florida and Texas

The δ³⁴S values of dissolved sulfide and the sulfur isotope fractionations between dissolved sulfide and sulfate species in Floridan ground water generally correlate with dissolved sulfate concentrations which are related to flow patterns and residence time within the aquifer. The dissolved sulfide derives from the slow in situ biogenic reduction of sulfate dissolved from sedimentary gypsum in the aquifer. In areas where the water is oldest, the dissolved sulfide has apparently attained isotopic equilibrium with the dissolved sulfate (Δ³⁴S = 65 per mil) at the temperature (28°C) of the system. This approach to equilibrium reflects an extremely slow reduction rate of the dissolved sulfate by bacteria; this slow rate probably results from very low concentrations of organic matter in the aquifer.In the reducing part of the Edwards aquifer, Texas, there is a general down-gradient increase in both dissolved sulfide and sulfate concentrations, but neither the δ³⁴S values of sulfide nor the sulfide-sulfate isotope fractionation correlates with the ground-water flow pattern. The dissolved sulfide species appear to be derived primarily from biogenic reduction of sulfate ions whose source is gypsum dissolution although upgradient diffusion of H₂S gas from deeper oil field brines may be important in places. The sulfur isotope fractionation for sulfide-sulfate (about 38 per mil) is similar to that observed for modern oceanic sediments and probably reflects moderate sulfate reduction in the reducing part of the aquifer owing to the higher temperature and significant amount of organic matter present; contributions of isotopically heavy H₂S from oil field brines are also possible.     

Geochemical and isotopic investigation of the aquifer system in the Djerid-Nefzaoua basin, southern Tunisia

In the Djerid-Nefzaoua region, southern Tunisia, about 80% of agricultural and domestic water supply is provided by the complex terminal (CT) aquifer. However, 20% of this demand is provided by other hydraulically connected aquifers, namely the continental intercalaire (CI) and the Plio-Quaternary (PQ). Overexploitation of the CT aquifer for agricultural practices has contributed to the loss of the artesian condition and the decline of groundwater level which largely increased the downward leakage from the shallow PQ aquifer. Excess irrigation water concentrates at different rates in the irrigation channels and in the PQ aquifer itself. Then, it returns to the CT aquifer and mixes with water from the regional flow system, which contributes to the salinization of the CT groundwater. A geochemical and isotopic study had been undertaken over a 2-years period in order to investigate the origin of waters pumped from the CT aquifer with an emphasis on its hydraulic relationships with the underlying and the overlying CI and PQ aquifers. Geochemistry indicates that groundwater samples collected from different wells show an evolution of the water types from Na-Cl to Ca-SO₄-Cl. Dissolution of halite, gypsum and anhydrite-bearing rocks is the main mechanism that leads to the salinization of the groundwater. Isotopic data indicate the old origin of all groundwater in the aquifer system. Mixing and evaporation effects characterizing the CT and the PQ aquifers were identified using δ²H and δ¹⁸O relationship and confirmed by the conjunction of δ²H with chloride concentration.     

Review: The potential impact of underground geological storage of carbon dioxide in deep saline aquifers on shallow groundwater resources

Underground geological storage of CO₂ in deep saline aquifers is considered for reducing greenhouse gases emissions into the atmosphere. However, some issues were raised with regard to the potential hazards to shallow groundwater resources from CO₂ leakage, brine displacement and pressure build-up. An overview is provided of the current scientific knowledge pertaining to the potential impact on shallow groundwater resources of geological storage of CO₂ in deep saline aquifers, identifying knowledge gaps for which original research opportunities are proposed. Two main impacts are defined and discussed therein: the near-field impact due to the upward vertical migration of free-phase CO₂ to surficial aquifers, and the far-field impact caused by large-scale displacement of formation waters by the injected CO₂. For the near-field, it is found that numerical studies predict possible mobilization of trace elements but concentrations are rarely above the maximum limit for potable water. For the far-field, numerical studies predict only minor impacts except for some specific geological conditions such as high caprock permeability. Despite important knowledge gaps, the possible environmental impacts of geological storage of CO₂ in deep saline aquifers on shallow groundwater resources appears to be low, but much more work is required to evaluate site specific impacts.     

Geochemical (process based) characterization of groundwater along the KT boundary of South India

A study has been carried out in KT (Cretaceous-Tertiary) boundary along the contact zones of hard rock, limestone and sedimentary formations to discern the geochemical processes governing the groundwater chemistry. A total of sixty-three groundwater samples were collected from the handpumps covering the entire study area and measured for hydrochemical species. Principal component analysis of the hydrochemical data inferred three major processes governing the geochemistry of the groundwater of the region as leaching, ion exchange and weathering. It was also inferred that there are few samples depicting the mixtures of these processes (what are they mention it) and few samples not representing any of these processes with adequate statistical significance. Hence, in order to know the geochemical behaviour of the samples representing each process, their combinations along with the samples which are not- representative samples of these processes were inferred using various standards plots to get an insight into their geochemical characteristics and affinity. This also inferred the samples representing different processes have a significant signature of geochemical facies. The major ions and the stable isotopes of groundwater were used to understand these processes. The carbonate and sulphate saturation states of these samples were calculated by PHREEQC and compared with major variations with the identified three geochemical processes. The state of saturation of Halite, Anhydrite, Gypsum, Aragonite, Dolomite, Calcite, Talc and Chrysolite were determined in all the samples. Inverse modeling was carried out considering the non-representative samples as initial solution and the samples representing each factor as final solution to understand the phase mole transfer in each process. An attempt was also made in this study to compare the geochemical behaviour of groundwaters from different KT boundaries. The samples representing these processes were plotted on an integrated map representing lithology, lineaments, drainage and elevation to determine their interrelationships. The study groups the samples into anthropogenic or geogenic. The leaching process is controlled by lithology and landuse, ion exchange processes is influenced by lithology and drainage patterns whereas weathering processes were controlled by lithology, drainage and lineaments. Non representation of samples (NRS) were mainly controlled by drainage and lineaments of the region.