Aquitard Porewater Research Articles

Salinity evolution of aquitard porewater associated with transgression and regression in the coastal plain of Eastern China

Aquitards can preserve paleo-saltwater and have a long and profound influence on the aquifer groundwater, yet they have received less attention. Here, five one-dimensional vertical profiles of the natural tracers, Cl−, Br−, δ2H, and δ18O of aquitard porewater were measured and combined with eight existing profiles collected from previous studies in three Eastern China coastal plains, Bohai bay, Laizhou bay, and Jiangsu coastal plain, to show the salinity origin and the timescale of the transport of porewater across aquitards since the mid-Holocene. Evidence of paleo-seawater impacted by Holocene transgression is noticed as peak Cl− concentration, enriched water isotopes, and lower Cl/Br ratios are observed in the porewater at about the bottom depth of Holocene of 25 m. The shape of Cl− profiles and associated 1-D transport models confirms Holocene seawater's presence in the sediment and the alternating transgression and regression control the salinity evolution of coastal aquitard porewater. Diffusion is the dominant transport across aquitard with an upward velocity between 0.03 and 0.6 mm/yr. Reverse advective flow has affected the solute transport in areas of extensive pumping. Anthropogenic activities enhance the leaching of salty porewater into aquifers in coastal areas, necessitating the need for research focused on marine aquitard salty water.

Controls on distributions of sulphate, fluoride, and salinity in aquitard porewater from the North China Plain: Long-term implications for groundwater quality

Groundwater interacts with porewater within clay-rich sequences. However, the effects of aquitard porewater on groundwater quality are generally poorly understood. This study explores potential links between porewater chemistry in a thick clay-rich sequence of Quaternary sediments, and groundwater quality in the North China Plain (NCP), one of China’s most important water supply aquifers. Previous studies have hypothesised the release of salinity, fluoride, and sulphate from aquitards in response to intensive pumping, without explicitly analysing the chemistry of aquitard porewaters. This study further investigated this hypothesis through targeted analysis of porewater chemistry profiles through the NCP sedimentary sequence. Two cores were analysed – one in the central plain (Hengshui, HS) and the other in the coastal plain (Cangzhou, CZ). Both areas have experienced significant groundwater extraction over recent decades from confined aquifers inter-layered with clays. Aqueous extraction (AE) and squeezing (SE) methods were both used to assess porewater chemistry. The hydrochemical characteristics of groundwater are closer to those of the squeezed porewater, which can be regarded as more closely corresponding to in-situ porewater compositions than AE profiles. Chloride was generally consistent between the two methods, while sulphate and fluoride concentrations were greater using AE, ranging from 340 to 48,700 mg/L and 8.8 to 144 mg/L, compared to 350 to 8860 mg/L and 0.2 to 4.3 mg/L using SE, respectively. The much greater concentrations of fluoride derived from the AE method indicates a high susceptibility to release during changes to the ambient geochemical environment. While the primary fluoride sources in groundwater and porewater are likely minerals from weathering of volcanic rocks in the sedimentary sequence, release into groundwater appears linked to common geochemical influences such as high Na/Ca ratio (increased during cation exchange) and the presence of iron and aluminium oxides (providing sorption sites). The primary source of solutes is interpreted to be different in each profile, with evapotranspiration important in the central plain and marine solutes important in the coastal profile, indicating significant storage of salinity, fluoride, and sulphate within low permeability sediments. Our data supports the hypothesis that release of these ions is driving degradation of groundwater quality, in response to decades of intensive groundwater extraction, which is an ongoing threat to the quality of groundwater in the NCP.

Carbon and methane cycling in arsenic-contaminated aquifers

Geogenic arsenic (As) contamination of groundwater is a health threat to millions of people worldwide, particularly in alluvial regions of South and Southeast Asia. Mitigation measures are often hindered by high heterogeneities in As concentrations, the cause(s) of which are elusive. Here we used a comprehensive suite of stable isotope analyses and hydrogeochemical parameters to shed light on the mechanisms in a typical high-As Holocene aquifer near Hanoi where groundwater is advected to a low-As Pleistocene aquifer. Carbon isotope signatures (δ13C-CH4, δ13C-DOC, δ13C-DIC) provided evidence that fermentation, methanogenesis and methanotrophy are actively contributing to the As heterogeneity. Methanogenesis occurred concurrently where As levels are high (>200 µg/L) and DOC-enriched aquitard pore water infiltrates into the aquifer. Along the flowpath to the Holocene/Pleistocene aquifer transition, methane oxidation causes a strong shift in δ13C-CH4 from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers.

Effects of ultrafiltration on salt migration and isotopic composition of pore water in groundwater depression area in Hengshui, NCP

AbstractClay aquitards are semipermeable membranes that allow groundwater flow while retarding solute migration has been researched extensively but also subjected to much debate. At present, there is no evidence of whether the physical and chemical properties of clay soil and the isotopic composition of pore water affect the semipermeable membrane effect. In this study, we collected clay samples from drilling cores (30–90 m) in the Hengshui area located in the North China Plain (NCP), then extracted pore water using a high‐pressure squeezing device. Vertical hydrochemical and isotopic profile variation trends for the pore water were revealed using hydrochemical (Cl−, Na+, Ca2+, K+, Mg2+, and SO42−) and stable isotopic measurements of H, O and Cl. The results showed that the hydrochemical clay interlayer pore water of the saline aquifer is Cl/SO4‐Na/Mg type and the average total dissolved solids (TDS) are 10.17 g/L. However, the hydrochemical clay aquitard pore water is of the Cl/SO4‐Na/Ca type with an average TDS of 1.90 g/L. The hydrochemical clay interlayer pore water of aquifer II is of Cl‐Na/Ca type with an average TDS of 1.10 g/L. Our results showed that the water quality of the aquifer II is not affected by the upper part of the saline aquifer, thus the clay aquitard acts as a significant barrier to salt movement. A polarization layer concentrated in ions was formed between the upper part of the saline aquifer and the clay aquitard. The concentration polarization layer increases the salt‐inhibition effect. H, O and Cl isotopic composition results showed significant fractionation. The pore water of aquifer II lacked heavy isotopes (2H, 18O, 37Cl), but had significant heavy isotope enrichment in the concentrated polarized layer (the δ2H value was −76‰, the δ18O value was −8.4‰, and the δ37Cl value was 1.59‰). Hyperfiltration thus played a significant role in isotope fractionation.

Groundwater Salinization and Flushing During Glacial‐Interglacial Cycles: Insights From Aquitard Porewater Tracer Profiles in the North China Plain

AbstractUsing natural tracer profiles to study migration of porewater salinity can help determine fluid fluxes and the timescales of salinization and freshening in coastal regions. Saline groundwater associated with evaporation and transgression events is widely distributed in the North China Plain (NCP). However, the fluid flux, time scales, and importance of different salinization processes are poorly constrained, particularly in areas beyond the limit of marine influence. Chloride (Cl) and δ18O profiles were obtained from two boreholes: one drilled at the edge of the piedmont alluvial fan (HS borehole) and one in the coastal region (G1 borehole). Numerical simulation of Cl and δ18O profiles confirmed diffusion‐dominated solute transport but also indicated slow upward advective flow over geological timescales. The profile modeling at HS indicated that salinization related to evaporation has occurred since the Late Pleistocene. Assessment of alternative conceptual models indicates that intensive groundwater pumping in recent decades has also caused significant downward movement of saline porewater (e.g., movement of brackish water at ~0.6 m/yr), mixing modern or Holocene water with Pleistocene water. The coastal Cl profile modeling in contrast shows that porewater salinity can be primarily attributed to salt diffusion during four transgression/regression cycles since the late Middle Pleistocene. The Cl transport appears never to have reached an equilibrium state during the glacial‐interglacial cycles. This suggests not only that trapped Holocene seawater is still present and leaching into adjacent sediments but also that Pleistocene water has never been entirely flushed from the deep part of the coastal sediments.

Contribution of clay-aquitard to aquifer iron concentrations and water quality

The contribution of aquitards to aquifer water quality can be pronounced but is rarely considered. The aims of this study were to delineate the spatial distribution of iron in a shallow aquitard-aquifer system within Jianghan Plain (JHP) of central China and to identify the origin of high iron within aquifers. Infiltration, hydraulic gradients and sediment chemistry influence the distribution of iron in the aquitard pore water which has a significant effect on the underlying aquifer. Chemical equilibrium modeling of pore water was used to simulate chemical processes influencing aquifer chemistry and determined the possible precipitation of FeCO3, FeS minerals (FeSx) and Fe-oxides (representing hydroxides, oxyhydroxides, and oxides of ferric iron). We presented a conceptual chemical-physical scenario to explain the observed Fe distributions: (1) Increasing iron concentrations with low-level sulfide in aquitard pore water. (2) Increasing iron concentrations with low-level sulfide in aquitard pore water underlying ponded water. (3) Decreasing iron concentrations with high-level sulfide in aquitard pore water. In combination, our findings illustrate the influence of aquitards on aquifer chemistry using Fe within the Jianghan Plain as an example.

High chloride, sulphate and fluoride concentrations in clay-rich aquitard porewater, the North China Plain: evidence of geochemical behavior

The focus of this investigation was to constrain the porewater chemistry from tracer and ion profiles in a 128 m thick clay-rich sequence of Quaternary sediments comprising the clay, silt and fine sand formation in the North China Plain. Porewater are much more saline (1.1-71.0 g/L) than the lower confined groundwaters (0.3-1.3g/L). Chloride profiles from aqueous extraction (AE) (ranging from 117 to 3260 mg/L) generally keep good consistent with that obtained from squeezing test (ST). However, the sulphate and fluoride concentrations by AE (ranging from 340 to 48,700 mg/L and from 8.8 to 144 mg/L, respectively) are far greater than that by ST. Dissolution of evaporites may be responsible for the high Cl/Br ratios greater than 1000, probably indicating recharge occurred during much wetter periods. The original stable isotopic and chemical compositions in the aquitard porewater have been modified by transpiration and evaporation processes concentrating Cl and causing isotopic enrichment during their formation periods. Dissolution of fluorite, hieratite, and cryolite caused by weathering behavior and ion-exchange reactions should be responsible for the high fluoride concentrations in the aquitard porewater. High sulphate levels found in aqueous samples may arise from pyrite oxidation during sampling, storage and/or porewater extraction procedure.

Salinization of porewater in a multiple aquitard-aquifer system in Jiangsu coastal plain, China

Chemical and isotopic compositions were analyzed in porewater squeezed from a clayey aquitard in Jiangsu coastal plain, eastern China, to interpret the salinity origin, chemical evolution and water-mass mixing process. A strong geochemical fingerprint was obtained with an aligned Cl/Br ratio of 154 in the salinized aquitard porewater over a wide Cl− concentration range (396–9,720 mg/L), indicating that porewater salinity is likely derived from a mixing with old brine with a proportion of less than 20%. Very small contributions of brine exerted limited effects on water stable isotopes. The relationships between porewater δ18O and δD indicate that shallow and intermediate porewaters could be original seawater and were subsequently diluted with modern meteoric water, whereas deep porewaters with depleted stable isotopic values were probably recharged during a cooler period and modified by evaporation and seawater infiltration. The cation–Cl relationship and mineralogy of associated strata indicate that porewater has been chemically modified by silicate weathering and ion-exchange reactions. 87Sr/86Sr ratios of 0.7094–0.7112 further confirm the input source of silicate minerals. Numerical simulations were used to evaluate the long-term salinity evolution of the deep porewater. The alternations of boundary conditions (i.e., the third aquifer mixed with brine at approximately 70 ka BP, followed by recharge of glacial meltwater at 20–25 ka BP, and then mixing with Holocene seawater at 7–10 ka BP) are responsible for the shift in porewater salinity. These timeframes correspond with the results of previous studies on ancient marine transgression-regression in Jiangsu coastal plain.

Environmental Tracers in Groundwaters and Porewaters to Understand Groundwater Movement Through an Argillaceous Aquitard

Inter-aquifer leakage through an aquitard can be an important component of groundwater flow and can occur by diffuse leakage or via preferential pathways along secondary permeability features. In order to properly characterize inter-aquifer leakage it is desirable to use both porewater from the aquitard in conjunction with a regional investigation of groundwater in the aquifers. The aim of this study was to characterize inter-aquifer leakage through a regionally extensive aquitard between the Great Artesian Basin (GAB) and the deeper Arckaringa Basin of Australia. Chloride concentrations in the aquitard porewater profile indicates that transport through the aquitard is dominated by diffusion, but there is evidence at t least one location for increased interaquifer leakage due to secondary permeability features.

Origin and Geochemical Processes of Porewater in Clay-Rich Deposits in the North Jiangsu Coastal Plain, China

The hydrogeochemical and stable isotope compositions of aquitard porewater samples from three boreholes were investigated to determine the origin, salinization, and hydrochemical evolution of water in the North Jiangsu coastal plain, China. Three porewater groups were identified based on the water-bearing subsystems. The total dissolved solids (TDS) of porewater samples highly varied from 0.03 to 26.1 g/L. Molar Cl/Br ratios and δ18O and δ2H data indicate that the source of Group 1 salinized porewater was the Holocene seawater, whereas Group 3 salinized samples were probably related to the remnant palaeoseawater of the Late Pleistocene. Group 2 samples had low salinity (TDS < 1 g/L) and undetectable Br− concentrations, which were probably recharged during a colder period and without evidence of seawater involvement. The salinized porewater was likely diluted by freshwater, as evidenced by its depleted isotopes and low salinity relative to standard seawater. The ionic ratios and ionic deltas indicate that considerable water-rock interactions (e.g., cation exchange and mineral weathering) also accounted for the hydrochemical constituents of porewaters, and cation exchange seems to be more noticeable at low salinity.

Geochemistry of clayey aquitard pore water as archive of paleo-environment, western Bohai Bay

The record of paleo-environment in clayey aquitard pore water is much more effective relative to aquifer groundwater owing to the low permeability of clayey aquitard. Oxygen-18 ( 18 O), deuterium (D), and chemical patterns were determined in pore water samples extracted from two 500 m depth boreholes, G1 and G2, in western Bohai Bay, China. Shallow pore water samples (depth<102 m) are saline water, with the TDS (total dissolved solids) of 3.69-30.75 g/L, and deeper ones (depth=102-500 m) are fresh water, with the TDS<1 g/L. Content of major ions (i.e., Cl - , Na + , K + , Mg 2+ , SO4 2- , Ca 2+ ) is high in marine sediment pore water samples and gradually decrease towards to terres- trial sediment pore waters, together with the Cl/Br and Sr/Ba ratios changing significantly in different sedimentary facies along the study profile, indicating that pore water may be paleo-sedimentary water and not replaced by modern water. δ 18 O profile and positive correlation between δ 18 O and Cl - of shal- low saline pore water indicated diffusion as the main transport mechanism, and distinguished four transgressive layers since Late Quaternary (i.e., Holocene marine unit, two Late Pleistocene marine units and Middle Pleistocene marine unit), further supporting the finding that pore water retained the feature of paleo-sedimentary water. Climate was identified as the main influence on the isotopic signa- ture of aquitard pore waters and four climate periods were determined by δ 18 O profile.

Comparing vertical profiles of natural tracers in the Williston Basin to estimate the onset of deep aquifer activation

AbstractComparing high‐resolution depth profiles of different naturally occurring environmental tracers in aquitards should yield consistent and perhaps complementary information about solute transport mechanisms and the timing of major hydrogeological and climatological events. This study evaluated whether deep, continuous profiles of aquitard pore water chloride concentration could provide further insight into the paleohydrology of the Williston Basin, Canada, than possible using high‐resolution depth profiles of stable H/O isotopes of water (δ18O, δ2H). Pore water samples were obtained from extracts of cores taken over 392 m of the thick Cretaceous shale aquitard. Water samples were also collected from wells installed in the underlying regional sandy aquifer (Mannville Group; 93 m thick) and from seepage inflows into potash mine shafts (to 825 m below ground). Numerical modeling of the 1‐D vertical Cl− profile supported diffusion dominated solute transport in the shales. The modeling also showed a similar time frame for development of the Cl− profile prior to activation of the aquifer as determined from the δ18O profile (20–25 Ma); however, it provided a significantly longer and potentially better‐constrained time frame for evolution of the profile during the activation phase of the aquifer (0.5–1 Ma). The dominant paleoevent reflected in present‐day profiles of both tracers is the introduction of glaciogenic meteoric water to the Mannville aquifer underlying the shale during the Pleistocene. The source area of this water remains to be determined.

Palaeohydrogeological insights from natural tracer profiles in aquitard porewater, Great Artesian Basin, Australia

The value of using environmental tracer profiles in aquitards to quantify fluid flux and to reveal information about palaeohydrology is largely unknown for parts of the world that were not glaciated during the Cenozoic. We present deep, continuous vertical profiles of aquitard pore water chloride concentration and δ2H/δ18O composition from the western margin of the Great Artesian Basin, Australia, where upward leakage is the dominant groundwater discharge mechanism. At the deeper of the two sites studied, the Cl− and δ2H profiles exhibit a distinctive S‐shape, which we interpret as a shift in the upper concentration boundary condition over time. Numerical simulations are used to support an hypothesis that the shallow phreatic aquifer was more saline and more enriched in δ2H compared to current conditions prior to ∼120 ka, followed by an extended freshening phase from ∼120 to 20 ka, then a saline phase similar to current conditions for the last ∼20 ka. These timeframes correspond favorably with results of previous studies into the palaeohydrology of nearby playa Lake Eyre. At the shallower site, the tracer profiles decrease exponentially with depth. We explore several models for the evolution of these profiles and adopt one of long‐term salt input at ground surface. At both sites, tracer concentrations for groundwater sampled from the underlying artesian aquifer provide conclusive evidence that recharge occurred within the last 10–20 ka. Chloride was a more useful tracer than δ2H in this study, primarily due to lack of recent glaciation in central Australia to provide a dynamic δ2H tracer signal.

Contribution of the aquitard to the regional groundwater hydrochemistry of the underlying confined aquifer in the Pearl River Delta, China

Aquitards are capable of generating and preserving large amounts of chemicals. The release of the chemicals from the aquitards poses a potential contamination risk to groundwater that may be used as a drinking water source. This work aimed to identify the contribution of hydrogeochemical processes in the aquitards to groundwater hydrochemistry in the underlying confined basal aquifer by studying the coastal Quaternary aquifer–aquitard system of the Pearl River Delta, China. The system was submerged by paleo-seawater in the early Holocene and mainly receives infiltration of precipitation at present, as indicated by investigations on stable isotopes (δ2H, δ18O), water chemistry (SO42− and Cl−) and salinity. Significant correlations between total dissolved solids in the basal aquifer and the thickness of the overlying aquitard further suggested the contribution of the aquitard to the groundwater hydrochemistry in the aquifer. Significant correlations between the chloride concentrations in aquitard porewater and that in groundwater in the aquifer, and between the thickness of the aquitard and the chloride concentrations in groundwater indicated the strong influence of the aquitard on the chloride in the aquifer. This is probably because the low-permeability aquitard is capable of preserving the paleo-seawater in the aquifer and releasing the salinity from the aquitard down to the aquifer via downward flow or diffusion. Isotopic and geochemical studies revealed that the aquitard is also responsible for generating and preserving large amounts of naturally occurring ammonium. Analysis between the concentrations of ammonium in groundwater in the basal aquifer and the total available ammonium in aquitard sediments suggested that the former is significantly controlled by the latter.

Geochemical signature of aquitard pore water and its paleo-environment implications in Caofeidian Harbor, China

Oxygen-18 (18O), deuterium (D), and chemical patterns were determined in pore water samples extracted from 100-m depth in Caofeidian Harbor, China. The stable isotopic composition indicates that aquitard pore water was of meteoric origin and was basically not influenced by evaporation. Seawater diffusion was identified as the main influence on the isotope signature of pore water, according to the δ18O profile and positive correlation between δ18O and Cl–. The chemistry of aquitard pore water is characterized by high total dissolved solids (TDS) decreasing with depth, ranging from 26.89 to 7.26 g/L. The same trend was observed for Cl–, Na+, and Mg2+, as influenced by seawater. However, the typical ion ratios (i.e., Cl/Br, Sr/Ba) of pore water change significantly in different sedimentary facies along the study profile due to the long-term reaction between pore water and sediment, further supporting the finding that pore water was not replaced by modern water or seawater. Therefore, during long-term aquitard residence, the chemical composition of pore water would be influenced by other processes such as reduction of sulfates and cation exchange. The rare earth elements (REEs) of pore water are mainly affected by water–rock interaction. The shale-normalized REE fractionation patterns display enrichment of heavy REEs (HREE) relative to light REEs (LREE) and even greater fractionation degree in marine sediment pore waters (as larger La/YbNASC). The relative reduction environment in the aquitard and preferential mobilization of Eu2+ in the water–rock interaction lead to the development of positive Eu anomalies (1.13 < (Eu/Eu*)NASC < 1.98) and slightly positive Ce anomalies (–0.13 < (Ce/Ce*)NASC < 0.35).

Using excess 4He to quantify variability in aquitard leakage

Fluid flux through aquitards controls the rate of recharge, discharge, cross-formational fluid flow and contaminant transport in subsurface systems. In this paper, concentrations of 4He are used to investigate the spatial distribution of vertical fluid flux through the regionally extensive Great Artesian Basin aquitard system in northern South Australia. Two vertical profiles of 4He concentration in aquitard pore water, augmented with regional sampling of aquifers above and below the aquitard were used to estimate fluid flux at multiple locations over a large spatial area. 4He concentrations in the shallow aquifer above the Great Artesian Basin range from atmospheric equilibrium to 1000 times enriched over atmosphere. Fluid flux through the aquitard was estimated by fitting observed helium concentrations at each sampling site with a 1-D model of helium transport through the aquitard. Estimated fluid fluxes through the aquitard vary over three orders of magnitude across the study area. In areas of competent aquitard, fluid fluxes are less than 0.003 mm/yr, and mass transport of helium is dominated by molecular diffusion. Preferential discharge zones are clearly identifiable with fluid fluxes up to 3 mm/yr. Our results show that fluid flux through a regionally extensive aquitard can be highly variable at large spatial scales, and that 4He concentrations in aquifers bounding the aquitard system provide a convenient and sensitive method for investigating aquitard flux at the regional scale.