Distribution of nitrate in groundwater affected by the presence of an aquitard at an agricultural area in Chiba, Japan

Geological and geographical parameters including land use, stratigraphic structure, groundwater quality, and N- and O-isotopic compositions of nitrate in groundwater were investigated to elucidate the mechanism of groundwater pollution by NO₃ ^? in the agricultural area of Katori, Chiba, Japan. An aquitard distributed in the western part of the study area has produced two unconfined aquifers. The average concentrations of NO₃ ^? and dissolved oxygen (DO) were high in the aquifer above the aquitard (7.5 and 7.6 mg/L, respectively) and in the aquifer of the eastern part of the study area that was not influenced by the aquitard (11.9 and 7.8 mg/L, respectively); however, the levels in the aquifer under the aquitard were relatively low (2.2 and 3.7 mg/L, respectively). The δ¹⁵N and δ¹⁸O values of NO₃ ^? generally increased exponentially in the groundwater that flowed into the aquifer under the aquitard as the concentration of NO₃ ^? decreased, although this decrease in NO₃ ^? also occasionally occurred without isotopic changes. These results indicated that the aquitard prevented the penetration of NO₃ ^?, DO, and gaseous O₂. Under the aquitard, denitrification and dilution with unpolluted water that entered from natural forested areas reduced the NO₃ ^? concentrations in the groundwater. The major sources of NO₃ ^? in groundwater in the study area were estimated to be NH₄-chemical fertilizer, livestock waste, and manure.     

Nitrogen and oxygen isotopic compositions of water-soluble nitrate in Taihu Lake water system, China: implication for nitrate sources and biogeochemical process

The stable isotope nitrogen-15 (¹⁵N) is a robust indicator of nitrogen (N) source, and the joint use of δ¹⁵N and δ¹⁸O–NO₃ ^? values can provide more useful information about nitrate source discrimination and N cycle process. The δ¹⁵N and δ¹⁸O–NO₃ ^? values, as well as major ion tracers, from Taihu Lake in east China were investigated to identify the primary nitrate sources and assess nitrate biogeochemical process in the present study. The results show that the nitrate concentration in West Taihu Lake (WTL) was generally higher than those in East Taihu Lake (ETL) and its upstream inflow rivers. The NO₃ ^?/Cl^? value combined with mapping of δ¹⁵N–NO₃ ^? and NO₃ ^? concentration suggest that the mixing process should play a major effect in WTL, and denitrification was the dominant N transformation process in WTL. A linear relationship of close to ~1: 2 was observed between δ¹⁵N–NO₃ ^? and δ¹⁸O–NO₃ ^? values in WTL, confirming the occurrence of denitrification in WTL. The δ¹⁵N–NO₃ ^? data imply that sewage and manure were the principal nitrate sources in WTL and its feeder rivers, while the nitrate in ETL might derive from soil organic nitrogen and atmospheric deposition. The δ¹⁸O–NO₃ ^? data indicate most of nitrate from microbial nitrification of organic nitrogen matter possibly make a significant contribution to the lake.     

Nitrate distribution and potential attenuation mechanisms of a municipal water supply bedrock aquifer

The Silurian bedrock aquifer constitutes a major aquifer system for groundwater supply across the Ontario province in Canada. The application of natural and industrial fertilizers near urban centers has led to groundwater NO₃⁻-N concentrations that sometimes have exceeded the drinking water limit, posing a threat to the usage of groundwater for the human consumption. Therefore, there is a growing interest and concern about how nitrate is being leached, transported and potentially attenuated in bedrock aquifers. This study assesses the local distribution of groundwater NO₃⁻ in the up-gradient area of two historically impacted municipal wells, called Carter Wells, in the City of Guelph, Canada, in order to evaluate the potential nitrate attenuation mechanisms, using both groundwater geochemical and isotopic analysis (³H, δ¹⁵N-NO₃, δ¹⁸O-NO₃, δ¹⁸O-SO₄, δ³⁴S-SO₄) and a detailed vertical hydrogeological and geochemical bedrock characterization. The results indicate that probably the main source of nitrate to the Carter Wells is the up-gradient Arkell Research Station (ARS), an agricultural research facility where manure has been historically applied. The overburden and bedrock groundwater with high NO₃ concentrations at the ARS exhibits a manure-related δ¹⁵N and δ¹⁸O signature, isotopically similar to the high nitrate in the down-gradient groundwater from domestic wells and from the Carter Wells. The nitrate spatial distribution appears to be influenced and controlled by the geology, in which more permeable rock is found in the Guelph Formation which in turn is related to most of the high NO₃⁻ groundwater. The presence of an underlying low permeability Eramosa Formation favors the development of oxygen-depleted conditions, a key factor for the occurrence of denitrification. Groundwater with low NO₃⁻-N concentrations associated with more oxygen-limited conditions and coincident with high SO₄²⁻ concentrations are related to more enriched δ¹⁵N and δ¹⁸O values in NO₃⁻ and to more depleted δ³⁴S and δ¹⁸O values in SO₄²⁻, suggesting that denitrification coupled with pyrite oxidation is taking place. The presence of macro crystalized and disseminated pyrite especially in the Eramosa Formation, can support the occurrence of this attenuation process. Moreover, based on tritium analysis, some denitrification can occur in shallow bedrock and within relatively short residence times, associated with less permeable conditions in depth which facilitates oxygen consumption through sulfide oxidation. The role of denitrification mediated by organic carbon cannot be discarded at the study site. This study suggests that the geological configuration and particularly the presence of low permeability Eramosa Formation can play an important role on nitrate natural attenuation, which may serve as a decision factor on defining the bedrock water supply system for both domestic and municipal purposes.     

Hydrogeochemical and isotopic evolution of water in the Complexe Terminal aquifer in the Algerian Sahara

The hydrogeochemical and isotopic evolution of groundwaters in the Mio–Pliocene sands of the Complexe Terminal (CT) aquifer in central Algeria are described. The CT aquifer is located in the large sedimentary basin of the Great Oriental Erg. Down-gradient groundwater evolution is considered along the main representative aquifer cross section (south–north), from the southern recharge area (Tinrhert Plateau and Great Oriental Erg) over about 700 km. Groundwater mineralisation increases along the flow line, from 1.5 to 8 g l^?1, primarily as a result of dissolution of evaporite minerals, as shown by Br/Cl and strontium isotope ratios. Trends in both major and trace elements demonstrate a progressive evolution along the flow path. Redox reactions are important and the persistence of oxidising conditions favours the increase in some trace elements (e.g. Cr) and also NO₃ ^?, which reaches concentrations of 16.8 mg l^?1 NO₃-N. The range in ¹⁴C, 0–8.4 pmc in the deeper groundwaters, corresponds with late Pleistocene recharge, although there then follows a hiatus in the data with no results in the range 10–20 pmc, interpreted as a gap in recharge coincident with hyper-arid but cool conditions across the Sahara; groundwater in the range 24.7–38.9 pmc signifies a distinct period of Holocene recharge. All δ¹⁸O compositions are enriched relative to deuterium and are considered to be derived by evaporative enrichment from a parent rainfall around ?11‰ δ¹⁸O, signifying cooler conditions in the late Pleistocene and possibly heavy monsoon rains during the Holocene.     

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer,Sfax, southeastern Tunisia

Major element concentrations and stable (δ¹⁸O and δ²H) and radiogenic (³H and ¹⁴C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water–rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ¹⁸O and δ²H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO₄ and Ca-Na-Cl-SO₄. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ¹⁸O and δ²H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

     

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO₃-N (74–83 mg L^?1). The δ¹⁵N-NO₃ values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ¹⁵N-NO₃ values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ¹⁵N-NO₃ and δ¹⁸O-NO₃ values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between ?4.8 and ?7.9‰ and O isotope enrichment factors varying between ?3.8 and ?4.9‰. Similar δD and δ¹⁸O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10–20 years) than in the north (20–30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.     

Distribution of δ~(34)S and δ~(18)O in SO_4~(2-) in Groundwater from the Ordos Cretaceous Groundwater Basin and Geological Implications

<正>The Ordos Cretaceous Groundwater Basin,located in an arid-semiarid area in northwestern China,is a large-style groundwater basin.SO_4~(2-) is one of the major harmful components in groundwater.Dissolved SO_4~(2-) concentrations,andδ~(34)S-SO_4~(2-) andδ~(18)O-SO_4~(2-) in groundwater from 14 boreholes and in gypsum from aquifer were analyzed.Results show that SO_4~(2-) in shallow groundwaters originates from precipitation,sulfide oxidation,and dissolution of stratum sulphate,with a big range ofδ~(34)S values,from-10.7‰to 9.2‰,and addition of SO_4~(2-) in deep groundwater results from dissolution of stratum sulphate,with biggerδ~(34)S values,from 7.8‰to 18.5‰,compared with those in shallow groundwater.This research also indicates that three types of sulphate are present in the strata,and characterized by highδ~(34)S values and highδ~(18)O values-style,highδ~(34)S values and middleδ~(18)O valuesstyle, middleδ~(34)S values and lowδ~(18)O values-style,respectively.Theδ~(34)S-SO_4~(2-) andδ~(18)O-SO_4~(2-) in groundwater have a good perspective for application in distinguishing different groundwater systems and determining groundwater circulation and evolution in this area.     

Localized zones of denitrification in a floodplain aquifer in southern Wisconsin, USA

A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O₂, Cl^?, NO ₃ ^? , SO ₄ ^2? , dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ¹⁵N_NO3 and δ¹⁸O_NO3 composition. Samples in which NO ₃ ^? was too low for stable isotope analysis were analyzed for excess dissolved N₂. Groundwater NO ₃ ^? concentrations declined between the agricultural field and the discharge point. Chloride and δ¹⁵N_NO3/δ¹⁸O_NO3 data indicated that the drop in NO ₃ ^? was caused primarily by dilution of shallow NO ₃ ^? -rich water with deeper, NO ₃ ^? -depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ¹⁵N_NO3 and δ¹⁸O_NO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N₂. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO ₃ ^? is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.     

Hydrogeochemical investigation of surface and groundwater composition in an irrigated land in Central Tunisia

Major element concentrations, stable (δ¹⁸O and δ²H) and radiogenic (³H, ¹⁴C) isotopes determined in groundwater provided useful initial tracers for understanding the processes that control groundwater mineralization and identifying recharge sources in semi-arid Cherichira basin (central Tunisia).Chemical data based on the chemistry of several major ions has revealed that the main sources of salinity in the groundwaters are related to the water–rock interaction such as the dissolution of evaporitic and carbonate minerals and some reactions with silicate and feldspar minerals.The stable isotope compositions provide evidence that groundwaters are derived from recent recharge. The δ¹⁸O and δ²H relationships implied rapid infiltration during recharge to both the Oligocene and Quaternary aquifers, with only limited evaporation occurring in the Quaternary aquifer.Chemical and isotopic signatures of the reservoir waters show large seasonal evolution and differ clearly from those of groundwaters.Tritium data support the existence of recent recharge in Quaternary groundwaters. But, the low tritium values in Oligocene groundwaters are justified by the existence of clay lenses which limit the infiltration of meteoric water in the unsaturated zone and prolong the groundwater residence time.Carbon-14 activities confirm that groundwaters are recharged from the surface runoff coming from precipitation.     

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.     

Effect of diffuse recharge and wastewater on groundwater contamination in Douala,Cameroon

High water demand for domestic use in Douala with over 3 million inhabitants is met mainly by shallow groundwater. Field measurements and water sampling in January 2015 were carried out to examine the major controls on the groundwater composition and spatial view of ions in the water, timing of recharge and link between the recharge process and quality of the water. Fifty-two water samples were analysed for major ions and stable hydrogen and oxygen isotopes. Low pH values (3.61–6.92) in the groundwater indicated an acidic aquifer; thus, prone to acidification. The dominant water type was Na–Cl. Nitrate, which exceeded the WHO guide value of 50 mg/l in 22% of the groundwater, poses a health problem. Mass ratios of Cl^?/Br^? in the water ranged from 54 to 3249 and scattered mostly along the mixing lines between dilute waters, septic-tank effluent and domestic sewage. A majority of the samples, especially the high NO₃ ^? shallow wells, clustered around the septic-tank effluent-end-member indicating high contamination by seepage from pit latrines; hence, vulnerable to pollution. Stable isotopes in the groundwater indicated its meteoric origin and rapid infiltration after rainfall. The δ¹⁸O values showed narrow ranges and overlaps in rivers, springs, open wells and boreholes. These observations depict hydraulic connectivity, good water mixing and a homogeneous aquifer system mainly receiving local direct uniform areal recharge from rainfall. The rapid and diffused recharge favours the leaching of effluent from the pit toilets into the aquifer; hence, the high NO₃ ^? and Cl^? in shallow wells. Silicate weathering, ion exchange and leaching of waste from pit toilets are the dominant controls on the groundwater chemistry. Drilling of deep boreholes is highly recommended for good-quality water supply. However, due the hydraulic connection to the shallow aquifer, geochemical modelling of future effects of such an exploitation of the deeper aquifer should support groundwater management and be ahead of the field actions.     

Sources and Processes Affecting Nitrate in a Dam-Controlled Subtropical River,Southwest China

Excess nutrient (N and P) loads are recognized as the major cause of serious water quality problems in China. River systems play a very important role in nitrate (NO₃ ^?) transportation and transformation in the aquatic environment. To understand and clarify the sources and processes affecting NO₃ ^? in river basins, we have examined spatial and temporal variations of concentration and dual-isotopic composition of NO₃ ^? in the dam-controlled Jialing River, a major tributary of the Yangtze River where land use is dominated by agriculture. Water samples were collected in July 2008 and February 2009 from the main channel of the Jialing River and its major tributaries. The δ¹⁵N and δ¹⁸O of NO₃ ^? range from 1.5 to 11.0 ‰ (average 6.2 ‰) and ?5.0 to 11.1 ‰ (average, 1.6 ‰), respectively. NO₃ ^? isotope data and δ¹⁸O of water interpreted in combination with hydrological and chemical data suggest that most of the NO₃ ^? input is from nitrification during the rainy season, and discharge of sewage and manure in the upper course and from cities accounts for much of the NO₃ ^? load during the dry season. The construction of cascade dams has led to retention of Si and a decrease in the Si/N ratio, implying that assimilation and/or denitrification may significantly affect NO₃ ^? in the dam area, as demonstrated by NO₃ ^? and dissolved Si concentrations, and \(\updelta^{ 1 5} {\text{N}}_{{{\text{NO}}_{3} }}\) and \(\updelta^{ 1 8} {\text{O}}_{{{\text{NO}}_{3} }}\) values. This study indicates that dual-isotopic data can be used to identify NO₃ ^? pollution sources and the processes NO₃ ^? has undergone during its retention and transport in the watershed of the dam-controlled Jialing River.     

Biogeochemistry of nitrous oxide in groundwater in a forested ecosystem elucidated by nitrous oxide isotopomer measurements

The biological and physical controls on microbial processes that produce and consume N₂O in soils are highly complex. Isotopomer ratios of N₂O, with abundance of ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O, and ¹⁴N¹⁴N¹⁸O relative to ¹⁴N¹⁴N¹⁶O, are promising for elucidation of N₂O biogeochemistry in an intact ecosystem. Site preference, the nitrogen isotope ratio of the central nitrogen atom minus that of the terminal nitrogen atom, is useful to distinguish between N₂O via hydroxylamine oxidation and N₂O via nitrite reduction.We applied this isotopomer analysis to a groundwater system in a temperate coniferous-forested ecosystem. Results of a previous study at this location showed that the N₂O concentration in groundwater varied greatly according to groundwater chemistry, i.e. NO₃⁻, DOC, and DO, although apportionment of N₂O production to nitrification or denitrification was ambiguous. Our isotopic analysis (δ¹⁵N and δ¹⁸O) of NO₃⁻ and N₂O implies that denitrification is the dominant production process of N₂O, but definitive information is not derived from δ¹⁵N and δ¹⁸O analysis because of large variations in isotopic fractionations during production and consumption of N₂O. However, the N₂O site preference and the difference in δ¹⁵N between NO₃⁻ and N₂O indicate that nitrification contributes to total N₂O production and that most measured N₂O has been subjected to further N₂O reduction to N₂. The implications of N₂O biogeochemistry derived from isotope and isotopomer data differ entirely from those derived from conventional concentration data of DO, NO₃⁻, and N₂O. That difference underscores the need to reconsider our understanding of the N cycle in the oxic-anoxic interface.     

The isotopic composition of nitrate produced from nitrification in a hardwood forest floor

Dual isotopic analysis of nitrate (¹⁵N/¹⁴N and ¹⁸O/¹⁶O) is increasingly used to investigate the environmental impacts of human-induced elevated atmospheric nitrate deposition. In forested ecosystems, the nitrate found in surface water and groundwater can originate from two sources: (1) atmospheric deposition, and (2) nitrate produced from nitrification in forest soils (microbial nitrate). Application of the dual nitrate isotope technique for determining the relative importance of nitrate sources in forested catchments requires knowledge of the isotopic composition of microbial nitrate. We excluded precipitation inputs to three zero-tension lysimeters installed below the F-horizon (Oe) at the Turkey Lakes Watershed (TLW) in order to measure the isotopic composition of microbial nitrate produced in situ. To our knowledge, this is the first in situ study of the isotopic composition of microbial nitrate in forest soils. Over a 2-week period, nitrate produced by nitrification was periodically flushed to the lysimeters by watering the area with a nitrogen-free solution. Nitrate produced in the forest floor had δ¹⁸O values ranging from +3.1‰ to +10.1‰ with a mean of +5.2‰. These values were only slightly higher than from the expected value of +1.0‰ calculated for chemolithoautotrophic nitrification, which depends on the δ¹⁸O of available O₂ and H₂O. In addition to nitrate, we also collected soil gas to determine if soil respiration and O₂ diffusion affected soil gas δ¹⁸O-O₂, which is typically assumed to be identical to atmospheric O₂ (+23.5‰) when calculating microbial nitrate δ¹⁸O values. No significant difference in δ¹⁸O-O₂ from atmospheric O₂ was found in forest soils to a depth of 55 cm, and therefore ¹⁸O-enrichment of soil gas O₂ could not explain the modest enrichment of nitrate ¹⁸O. Evaporative ¹⁸O-enrichment of soil water available to nitrifiers in the forest floor is a plausible mechanism for slightly elevated nitrate δ¹⁸O values. However, the observed nitrate δ¹⁸O values could also be explained by a minor contribution of nitrate from heterotrophic nitrifiers. The δ¹⁵N of nitrate produced ranged from −10.4 to −7.3‰ and, as expected, was depleted in ¹⁵N relative to soil organic nitrogen. Microbial nitrate produced in the forest floor was also significantly depleted in ¹⁵N relative to microbial nitrate exported in groundwater and headwater streams at the TLW. We hypothesize that ¹⁵N-depleted forest floor nitrate is not detected in groundwaters largely because of: (1) the immobilization of forest floor nitrate in the mineral soil and (2) the mixing of the remaining forest floor nitrate with nitrate generated in the mineral soil, which is expected to have higher δ¹⁵N values. This study demonstrates that current methods of calculating a priori the δ¹⁸O of microbial nitrate provide a reasonable value for nitrate produced by nitrification at the TLW.     

Sources of dissolved ions revealed by chemical and isotopic tracers in the Geum River,South Korea

Water samples were collected in the main channel of the Geum River, South Korea, and measured dissolved elemental concentrations and isotopic compositions of nitrate in order to identify the factors controlling water chemistry. Elemental concentrations significantly increased location-wise after the confluence from urban areas, indicating the changes in solute sources from chemical weathering to anthropogenic inputs such as manure, fertilizers, and sewage. In particular, the effect of sewage input is manifested in the concentrations of Cl^?, SO₄ ^2?, and Na⁺, while the NO₃ ^? concentration is influenced mainly by soil inputs with minor contributions from manure and fertilizer because both δ¹⁵N–NO₃ and δ¹⁸O–NO₃ indicate NO₃ ^? mostly consists of soil-derived nitrates in the upper reaches but manure/sewage nitrates in the lower reaches. The relative proportion of three factors, Cl^?, Ca²⁺+Mg²⁺, and NO₃ ^?, indicates that water chemistry in the upstream is controlled by the soil weathering but that in the downstream by the sewage. Seasonally, water chemistry during summer is dominated by the soil weathering due to the flushing effect but that during winter by the sewage. This study suggests that the relative proportion of three factors can be used for tracing natural and anthropogenic sources in water chemistry.     

Residence time of Chalk groundwaters in the Paris Basin and the North German Basin: a geochemical approach

The comparative geochemical and isotopic study of confined and unconfined Chalk groundwaters of the Paris Basin and the N German Basin proves a significant chemical evolution during groundwater flow from the recharge zones to the deep confined aquifer. Different time dependent geochemical parameters have been tested as dating tools: Cation ratios (Sr²⁺/Ca²⁺, Mg²⁺/Ca²⁺), N–NO⁻₃, noble gas contents as paleotemperature indicators (Ne, Ar, Kr, Xe), radiogenic He, ¹³C, ¹⁴C, ¹⁸O, ²H, ³H. Cation ratios and ¹³C show the importance of incongruent dissolution processes in the Chalk aquifer. Water–rock interactions were taken into account in a multi-step dissolution model to determine radiocarbon groundwater ages. The oldest waters in the confined part of the Paris basin Chalk with maximum ¹⁴C ages of 14,000 a B.P. contain pleistocene recharge components as can be shown by a stable isotope depletion and noble gas temperatures significantly lower than in recent groundwaters. Chalk waters at the Lägerdorf site in Northern Germany show a distinct stratification with respect to residence times and hydrochemistry.     

Tracking sources of groundwater nitrate contamination using nitrogen and oxygen stable isotopes at Beijing area,China

The identification of sources and behavior of contaminants is important to control and manage groundwater quality of aquifer systems in urban areas. In this study, hydrogeochemistry of major constituents and stable isotope ratios of nitrate in groundwater were determined to identify contamination sources and transformation processes occurring in soils and deeper groundwater of Beijing with intense human activities. The nitrogen and oxygen isotopic compositions of nitrate in pore water extracts from groundwater samples indicate at least three potential sources of nitrate in groundwaters at Beijing. Stable isotope analyses from this study site, which has atmospheric, chemical fertilizer and human waste nitrate sources, provide a tool to distinguish nitrate sources in a confined aquifer where concentrations alone do not. These data indicate that the most common sources of high nitrate concentrations in groundwater at Beijing are wastewater and denitrification process occurred specially in the Central area. NO₃–N and cation and anion concentrations (Ca²⁺, Mg²⁺ Cl^? and SO ₄ ² ) showed strong correlations indicating that they originated from the same sources. This study demonstrates that a thorough evaluation of hydrodynamic and hydrochemical parameters with dual isotopes of NO₃ ^? constitutes an effective approach for identifying sources and transformation processes of NO₃ ^? in deeper groundwater systems.     

Evaluation of the origin and fate of nitrate in the Abbotsford Aquifer using the isotopes of15N and18O in NO3−

Extensive NO₃⁻ contamination of groundwater in the Abbotsford aquifer to levels above drinking water limits is a major problem in the Fraser Lowlands of southwestern British Columbia, Canada. Nitrate concentrations in the aquifer ranged from 0 to 151 mg/l NO₃⁻, with a median concentration of 46 mg/l NO₃⁻. Of 117 wells sampled, 54% had NO₃⁻ concentrations exceeding the drinking water limit of 45 mg/1. Approximately 80% of the study area had groundwater NO₃⁻ concentrations exceeding 40 mg/1 NO₃⁻. Potential NO₃⁻ source materials were poultry manure N and synthetic NH₄ based fertilizers. Theδ¹⁵N of solid poultry manure samples ranged between + 7.9 and + 8.6‰ (AIR). Four brands of synthetic fertilizers commonly used hadδ¹⁵N values between −1.5 and −0.6‰. Ammonia volatilization caused theδ¹⁵N of groundwater NO₃⁻ produced from poultry manure N to range between +8 and +16‰. Theδ¹⁸O values of groundwater NO₃⁻, by contrast, mostly ranged between +2 and +5‰ (SMOW). This narrow range ofδ¹⁸O values fell within the expected range of NO₃⁻ produced by nitrification of reduced N forms such as poultry manure N and NH₄ fertilizers, and had a similar range ofδ¹⁸O values as NO₃⁻ in the upper part of the unsaturated zone below raspberry fields and beneath former manure piles. Theδ¹⁵N-NO₃⁻ andδ¹⁸O-NO₃⁻ data confirmed that NO₃⁻ in the aquifer was predominantly derived from poultry manure and to a lesser extent from synthetic fertilizers. Theδ¹⁸O-NO₃⁻ data further suggested the nitrification process occurred mainly in the summer months, with the soil NO₃⁻ produced subsequently flushed into the aquifer during fall recharge. Theδ¹⁵N-NO₃⁻andδ¹⁸O-NO₃⁻ data conclusively indicated that no significant bacterial denitrification is taking place in the Abbotsford aquifer.     

An appraisal of groundwater quality in Seymour and Blaine aquifers in a major agro-ecological region in Texas,USA

Aquifer-based groundwater quality assessment offers critical insight into the major hydrochemical processes, and aids in making groundwater resources management decisions. The Texas Rolling Plains (TRP), spanning over 22 counties, is a major agro-ecological region in Texas from where highest groundwater nitrate (NO₃ ^?) levels in the state have been reported. In this study, we present a comparative assessment of major hydrochemical facies pertaining to NO₃ ^? contamination and a host of species such as sulfate (SO₄ ^2?), chloride (Cl^?), and total dissolved solids (TDS) in different water use classes in the Seymour and Blaine aquifers, underlying the TRP. Aquifer-stratified groundwater quality information from 1990 to 2010 was obtained from the Texas Water Development Board and aggregated over decadal scale. High groundwater salinization was found in the municipal water use class in the Blaine aquifer with about 100, 87 and 50 % of observations exceeding the secondary maximum contaminant level for TDS, SO₄ ^2?, and Cl^?, respectively in the 2000s (2000–2010). The NO₃-contamination was more alarming in the Seymour aquifer with 82 and 61 % of observations, respectively, exceeding the maximum contaminant level (MCL) in the irrigation and municipal water use classes in the 2000s. Salinization was more influenced by SO₄ ^2? and Cl^? in the Blaine aquifer and by NO₃ ^? in the Seymour aquifer. High NO₃ ^? (>MCL) observations in the Seymour aquifer occurred in the Ca–HCO₃ and Ca–Mg–HCO₃ facies, the domains of fresh water recharge and anthropogenic influences (e.g., agricultural activities, waste disposal). High SO₄ ^2?, Cl^? and TDS observations in the Blaine aquifer dominated the Ca–Cl, Na–Cl, and mixed Ca(Mg)–SO₄(Cl) facies indicating evaporite dissolution, mixing and solute exchange, and lack of fresh recharge.     

Tracing ionic sources and geochemical evolution of groundwater in the Intermountain Una basin in outer NW Himalaya,Himachal Pradesh,India

The present research aims to identify sources of ions and factors controlling the geochemical evolution of groundwater in an intermountain basin, comprising hill and valley fill region, of Outer Himalaya in Himachal Pradesh, India. The groundwater samples collected from 81 tubewells and handpumps are analyzed for major ions, trace metals and stable isotopes (δ¹⁸O and δD). Geochemically the dominant hydrochemical facies in the Una basin are Ca–HCO₃, Ca–Mg–HCO₃ and Na–Cl types at few locations. A relatively lower ionic concentration in the valley fills indicates dilution and low residence time of water to interact with the aquifer mass due to high porosity and permeability. The ionic ratios of 0.9, 0.8 and 3.8 to 5.7, respectively, for (Ca?+?Mg): HCO₃, (Ca?+?Mg): (HCO₃?+?SO₄) and Na: Cl, suggests that ionic composition of groundwater is mainly controlled by rock weathering of, particularly by dissolution/precipitation of calcrete and calcite hosted in rock veins and Ca–Na feldspar hosted in conglomerate deposits derived from the Higher and Lesser Himalaya during the formation of Siwalik rocks. Although Na, K, NO₃ and SO₄ are introduced in the groundwater through agricultural practices, Na has also been introduced through ion exchange processes that have occurred during water–rock interaction, as indicated by negative CAI values. Factor analysis further suggests three major factors affecting the water chemistry of the area. The first two factors are associated with rock weathering while the third is anthropogenic processes associated with high nitrate and iron concentration. High concentrations of Fe and Mn ions that are exceeded that of WHO and BIS standards are also present at few locations. The recharge of groundwater in the Outer Himalaya is entirely through Indian Southwest Monsoon (ISM) and depleted ratios of δ¹⁸O/δD in valley region indicate infiltration from irrigation in recharging the groundwater and fractionation of isotopes of precipitation due to evaporation before infiltration. High d-excess values and inverse relation with δ¹⁸O are indicative of secondary evaporation of precipitation during recharge of groundwater.