Origin of sulphate in the unsaturated zone and groundwater of a loess aquifer

The use of the sulphate mass balance (SMB) between precipitation and soil water as a supplementary method to estimate the diffuse recharge rate assumes that the sulphate in soil water originated entirely from atmospheric deposition; however, the origin of sulphate in soil and groundwater is often unclear, especially in loess aquifers. This study analysed the sulphur (δ³⁴S-SO₄) and oxygen (δ¹⁸O-SO₄) isotopes of sulphate in precipitation, water-extractable soil water, and shallow groundwater samples and used these data along with hydrochemical data to determine the sources of sulphate in the thick unsaturated zone and groundwater of a loess aquifer. The results suggest that sulphate in groundwater mainly originated from old precipitation. When precipitation percolates through the unsaturated zone to recharge groundwater, sulphates were rarely dissolved due to the formation of CaCO₃ film on the surface of sulphate minerals. The water-extractable sulphate in the deep unsaturated zone (>10 m) was mainly derived from the dissolution of evaporite minerals and there was no oxidation of sulphide minerals during the extraction of soil water by elutriating soil samples with deionized water. The water-extractable concentration of SO₄ was not representative of the actual SO₄ concentration in mobile soil water. Therefore, the recharge rate cannot be estimated by the SMB method using the water-extractable concentration of SO₄ in the loess areas. This study is important for identifying sulphate sources and clarifying the proper method for estimating the recharge rate in loess aquifers.     

Characterization of surface and ground water δ18O seasonal variation and its use for estimating groundwater residence times

¹⁸O is an ideal tracer for characterizing hydrological processes because it can be reliably measured in several watershed hydrological compartments. Here, we present multiyear isotopic data, i.e. ¹⁸O variations (δ¹⁸O), for precipitation inputs, surface water and groundwater in the Shingobee River Headwaters Area (SRHA), a well‐instrumented research catchment in north‐central Minnesota. SRHA surface waters exhibit δ¹⁸O seasonal variations similar to those of groundwaters, and seasonal δ¹⁸O variations plotted versus time fit seasonal sine functions. These seasonal δ¹⁸O variations were interpreted to estimate surface water and groundwater mean residence times (MRTs) at sampling locations near topographically closed‐basin lakes. MRT variations of about 1 to 16 years have been estimated over an area covering about 9 km² from the basin boundary to the most downgradient well. Estimated MRT error (±0·3 to ±0·7 years) is small for short MRTs and is much larger (±10 years) for a well with an MRT (16 years) near the limit of the method. Groundwater transit time estimates based on Darcy's law, tritium content, and the seasonal δ¹⁸O amplitude approach appear to be consistent within the limits of each method. The results from this study suggest that use of the δ¹⁸O seasonal variation method to determine MRTs can help assess groundwater recharge areas in small headwaters catchments. Copyright © 2005 John Wiley & Sons, Ltd.     

Temporal variation of stable isotopes in a precipitation–groundwater system: implications for determining the mechanism of groundwater recharge in high mountain–hills of the Loess Plateau,China

The groundwater in shallow loess aquifers in high mountain–hills in the western Loess Plateau in China is almost the sole water resource for local residents. However, the question about how the loess groundwater naturally circulates in these high mountain–hills, characterized by low precipitation and high potential evaporation, remains unclear. The objectives of this study are to evaluate the application of hydrogen and oxygen isotopes to (1) examine temporal variations of the isotopic composition of precipitation and shallow groundwater and (2) uncover the mechanism of groundwater recharge in high mountain–hills. Results from 2 years of monitoring data show a difference in the stable isotopes for groundwater and local precipitation between the winter and summer periods. Similar to precipitation, stable isotopes in groundwater are observed to be depleted in winter and enriched in summer, particularly in oxygen isotope. A prominent characteristic is that H and O isotopes of groundwater show a very clear response to strong precipitation in the rainy season in 2013. The results highlight that local precipitation is the likely recharge source for groundwater in shallow loess aquifers. Annual recharge from local precipitation maintains the groundwater resource in the shallower loess aquifer. The mechanisms governing shallow loess groundwater recharge in high mountain–hills were evaluated. In addition to possible vertical slow percolation of soil water through the unsaturated zone, rapid groundwater recharge mechanisms have been identified as temporal preferential infiltration through sinkholes, slip surface or landslide surface and through the interface of loess layer and palaeo‐soils. Most groundwater can be recharged after a heavy rainy season. Copyright © 2015 John Wiley & Sons, Ltd.     

Identification of groundwater recharge sources and processes in a heterogeneous alluvial aquifer: results from multi‐level monitoring of hydrochemistry and environmental isotopes in a riverside agricultural area in Korea

We evaluated sources and pathways of groundwater recharge for a heterogeneous alluvial aquifer beneath an agricultural field, based on multi‐level monitoring of hydrochemistry and environmental isotopes of a riverside groundwater system at Buyeo, Korea. Two distinct groundwater zones were identified with depth: (1) a shallow oxic groundwater zone, characterized by elevated concentrations of NO₃^? and (2) a deeper (>10–14 m from the ground surface) sub‐oxic groundwater zone with high concentrations of dissolved Fe, silica, and HCO₃^?, but little nitrate. The change of redox zones occurred at a depth where the aquifer sediments change from an upper sandy stratum to a silty stratum with mud caps. The δ¹⁸O and δ²H values of groundwater were also different between the two zones. Hydrochemical and δ¹⁸O? δ²H data of oxic groundwater are similar to those of soil water. This illustrates that recharge of oxic groundwater mainly occurs through direct infiltration of rain and irrigation water in the sandy soil area where vegetable cropping with abundant fertilizer use is predominant. Oxic groundwater is therefore severely contaminated by agrochemical pollutants such as nitrate. In contrast, deeper sub‐oxic groundwater contains only small amounts of dissolved oxygen (DO) and NO₃^?. The ³H contents and elevated silica concentrations in sub‐oxic groundwater indicate a somewhat longer mean residence time of groundwater within this part of the aquifer. Sub‐oxic groundwater was also characterized by higher δ¹⁸O and δ²H values and lower d‐excess values, indicating significant evaporation during recharge. We suggest that recharge of sub‐oxic groundwater occurs in the areas of paddy rice fields where standing irrigation and rain water are affected by strong evaporation, and that reducing conditions develop during subsequent sub‐surface infiltration. This study illustrates the existence of two groundwater bodies with different recharge processes within an alluvial aquifer. Copyright © 2009 John Wiley & Sons, Ltd.     

Isotope hydrology of the Allt a' Mharcaidh catchment,Cairngorms, Scotland: implications for hydrological pathways and residence times

The hydrology of oxygen‐18 (¹⁸O) isotopes was monitored between 1995 and 1998 in the Allt a' Mharcaidh catchment in the Cairngorm Mountains, Scotland. Precipitation (mean δ¹⁸O=−7·69‰) exhibited strong seasonal variation in δ¹⁸O values over the study period, ranging from −2·47‰ in the summer to −20·93‰ in the winter months. As expected, such variation was substantially damped in stream waters, which had a mean and range of δ¹⁸O of −9·56‰ and −8·45 to −10·44‰, respectively. Despite this, oxygen‐18 proved a useful tracer and streamwater δ¹⁸O variations could be explained in terms of a two‐component mixing model, involving a seasonally variable δ¹⁸O signature in storm runoff, mixing with groundwater characterized by relatively stable δ¹⁸O levels. Variations in soil water δ¹⁸O implied the routing of depleted spring snowmelt and enriched summer rainfall into streamwaters, probably by near‐surface hydrological pathways in peaty soils. The relatively stable isotope composition of baseflows is consistent with effective mixing processes in shallow aquifers at the catchment scale. Examination of the seasonal variation in δ¹⁸O levels in various catchment waters provided a first approximation of mean residence times in the major hydrological stores. Preliminary estimates are 0·2–0·8 years for near‐surface soil water that contributes to storm runoff and 2 and >5 years for shallow and deeper groundwater, respectively. These ¹⁸O data sets provide further evidence that the influence of groundwater on the hydrology and hydrochemistry of upland catchments has been underestimated. Copyright © 2000 John Wiley & Sons, Ltd.     

Combination of CFCs and stable isotopes to characterize the mechanism of groundwater–surface water interactions in a headwater basin of the North China Plain

Mountainous areas are characterized by steep slopes and rocky landforms, with hydrological conditions varying rapidly from upstream to downstream, creating variable interactions between groundwater and surface water. In this study, mechanisms of groundwater–surface water interactions within a headwater catchment of the North China Plain were assessed along the stream length and during different seasons, using hydrochemical and stable isotope data, and groundwater residence times estimated using chlorofluorocarbons. These tracers indicate that the river is gaining, due to groundwater discharge in the headwater catchment both in the dry and rainy seasons. Residence time estimation of groundwater using chlorofluorocarbons data reveals that groundwater flow in the shallow sedimentary aquifer is dominated by the binary mixing of water approximating a piston flow model along 2 flow paths: old water, carried by a regional flow system along the direction of river flow, along with young water, which enters the river through local flow systems from hilly areas adjacent to the river valley (particularly during the rainy season). The larger mixing ratio of young water from lateral groundwater recharge and return flow of irrigation during the rainy season result in higher ion concentrations in groundwater than in the dry season. The binary mixing model showed that the ratio of young water versus total groundwater ranged from 0.88 to 0.22 and 1.0 to 0.74 in the upper and lower reaches, respectively. In the middle reach, meandering stream morphology allows some loss of river water back into the aquifer, leading to increasing estimates of the ratio of young water (from 0.22 to 1). This is also explained by declining groundwater levels near the river, due to groundwater extraction for agricultural irrigation. The switch from a greater predominance of regional flow in the dry season, to more localized groundwater flow paths in the wet season is an important groundwater–surface water interactions mechanism, with important catchment management implications.     

Spatio‐temporal variability of the isotopic input signal in a partly forested catchment: Implications for hydrograph separation

The isotopic composition of precipitation (D and ¹⁸O) has been widely used as an input signal in water tracer studies. Whereas much recent effort has been put into developing methodologies to improve our understanding and modelling of hydrological processes (e.g., transit‐time distributions or young water fractions), less attention has been paid to the spatio‐temporal variability of the isotopic composition of precipitation, used as input signal in these studies. Here, we investigated the uncertainty in isotope‐based hydrograph separation due to the spatio‐temporal variability of the isotopic composition of precipitation. The study was carried out in a Mediterranean headwater catchment (0.56 km²). Rainfall and throughfall samples were collected at three locations across this relatively small catchment, and stream water samples were collected at the outlet. Results showed that throughout an event, the spatial variability of the input signal had a higher impact on hydrograph separation results than its temporal variability. However, differences in isotope‐based hydrograph separation determined preevent water due to the spatio‐temporal variability were different between events and ranged between 1 and 14%. Based on catchment‐scale isoscapes, the most representative sampling location could also be identified. This study confirms that even in small headwater catchments, spatio‐temporal variability can be significant. Therefore, it is important to characterize this variability and identify the best sampling strategy to reduce the uncertainty in our understanding of catchment hydrological processes.     

Flow dynamics of groundwater and soil water in the former heap Gessenhalde at the uranium mining area of Ronneburg: a stable isotope approach

Stable isotopes, ²H_water, ¹⁸O_water as well as ¹⁸O_sulphate and ³⁴S_sulphate, were used to study the flow system of shallow groundwater and soil water at the base area of a former leaching heap at the uranium mining area of Ronneburg, Germany. The flow paths and water‐retention times were estimated by comparison of δ²H and δ¹⁸O values in groundwater and soil water to the δ²H and δ¹⁸O signature of precipitation, giving distinctive inputs of summer or winter precipitation. The points of measuring the groundwater were divided into three categories with different flow conditions: rapid flow, stagnant conditions and a transition zone by hierarchical cluster analysis of δ²H and δ¹⁸O values of groundwater. The transit time of groundwater in the rapid flow area is less than 6 months, whereas water in the stagnant zone is stored for at least 1 year. In soil water, a clear response to different input signals is detectable only in the 30‐cm horizon (retention time is about 6 months), whereas at deeper levels a mixing with older water is taking place. The isotopic composition of the dissolved sulphate was used to identify oxidation of sulphides as the source of sulphate. Copyright © 2010 John Wiley & Sons, Ltd.     

Origin and type of rainfall for recharge of a karstic aquifer in the western Mediterranean: a case study from the Sierra de Gador–Campo de Dalias (southeast Spain)

Isotope signatures in precipitation from the Global Network for Isotopes in Precipitation around the Mediterranean basin and literature data are compared with isotopic data from a large karstic aquifer in southeast Spain to explain the origin and type of the precipitation events dominating recharge. Analysis of the deuterium excess d at the scale of the Mediterranean basin and at the regional scale allows us to understand the isotopic context of the study area: Campo de Dalias and the Sierra de Gador (Almería province). The origin of precipitation can be determined from its d value. The d value changes as a function of the initial evaporation condition. It depends on the relative humidity and temperature during the evaporation producing the water vapour of the clouds. The water vapour, which dominates the study area, is generated in two areas: the Atlantic Ocean (d = 10‰) and the western Mediterranean basin (d = 15‰). With increasing precipitation volume, the western Mediterranean character dominates. These heavier storms contribute mainly to recharge, as illustrated by the d value of 13·6‰ in deep groundwater of the Campo de Dalias. Weighted d values increase with the volume of precipitation, giving a significant relationship for the southern and eastern coasts of the Iberian Peninsula. This selectivity of d to monthly precipitation was used to estimate the return period of precipitation leading to aquifer recharge at 0·9–4·9 years. Moderate rainfall, which occurs more frequently, still represents ～60–90% of the total precipitation. One of the challenges to meet ever‐growing water demands is to increase recharge from moderate events yielding intermediate quantities per event, but forming the bulk of the annual precipitation. Copyright © 2006 John Wiley & Sons, Ltd.     

Using selected pharmaceutical compounds as indicators for surface water and groundwater interaction in the hyporheic zone of a low permeability riverbank

This study investigates the applicability of selected pharmaceutical compounds (e.g. sulfamethoxazole, carbamazepine, ibuprofen) as anthropogenic indicators for the interaction of surface water and groundwater in the hyporheic zone of an alluvial stream. Differences in transport behaviour and the resulting distribution of the pharmaceuticals in the riverine groundwater were evaluated. The investigated field site in the Grand Duchy of Luxembourg, Europe is represented by low permeable sediments and confined aquifer conditions. Water samples from single‐screen and multilevel observation wells installed in the riverbank at the field site were taken and analysed for selected pharmaceuticals and major ions for a period of 6 months. Surface water and groundwater levels were recorded to detect effluent and influent aquifer conditions. Nearly all pharmaceuticals that were detected in the stream were also found in the riverine groundwater. However, concentrations were significantly lower in groundwater than in surface water. A classification into mobile and sorbing/degradable pharmaceuticals based on their transport relevant properties was made and verified by the field data. Gradients with depth for some of these pharmaceuticals were documented and a more detailed understanding of the system stream/riverbank was obtained. It was demonstrated that the selected pharmaceutical compounds can be used as anthropogenic indicators at the investigated field site. However, not all compounds seem to be suitable indicators as their transport behaviour is not fully understood. Copyright © 2012 John Wiley & Sons, Ltd.     

Analytical and statistical approach for evaluating the effects of a river barrage on river–aquifer interactions

The construction of a river barrage can increase groundwater levels upstream of the barrage during the rainy season. Analytical and statistical approaches were applied to evaluate the relationship between groundwater and river water at the Changnyeong–Haman river barrage in Korea using time series data of water level and electrical conductivity from June 2011 to September 2014. An artificial neural network based time series model was designed to filter out the effect of rainfall from the groundwater level data in the study area. Aquifer diffusivity and river resistance were estimated from the analytical solution of a one‐dimensional unit step response function by using the filtered groundwater level data. River resistance increased in response to groundwater level fluctuations. Cross‐correlation analyses between the groundwater and the river water showed that the lag time increased during the observation period for both the water level and the electrical conductivity while the cross‐correlation function declined for the same period. The results indicated that a constant river stage maintained at the river barrage can weaken the hydrologic stress and reduce the exchange of material between the river and the adjacent aquifer because of the deposition of fine sediment on the river bottom and walls. Copyright © 2016 John Wiley & Sons, Ltd.