C-N elemental and isotopic investigation in agricultural soils: Insights on the effects of zeolitite amendments

In this paper we present an elemental and isotopic investigation of carbon and nitrogen in the soil-plant system. Plants grown in an unamended soil were compared to plants grown in a soil amended with natural and NH₄⁺-enriched zeolitites. The aim was to verify that zeolitites at natural state increase the chemical fertilization efficiency and the nitrogen transfer from NH₄⁺-enriched zeolitites to plants. Results showed that plants grown on plots amended with zeolitites have generally a δ¹⁵N approaching that of chemical fertilizers, suggesting an enhanced nitrogen uptake from this specific N source with respect to the unamended plot. The δ¹⁵N of plants grown on NH₄⁺-enriched zeolitites was strongly influenced by pig-slurry δ¹⁵N (employed for the enrichment process), confirming the nitrogen transfer from zeolitites to plants. The different agricultural practices are also reflected in the plant physiology as recorded by the carbon discrimination factor, which generally increases in plots amended with natural zeolitites, indicating better water/nutrient conditions.     

Nitrogen isotope studies of nitrate contamination of the thick vadose zones in the wastewater-irrigated area

The objective of this study was to investigate natural abundance and the distribution of nitrogen isotopic compositions to assess denitrification in two ~30 m thick vadose zones beneath the different land uses in the wastewater-irrigated area located in southern Shijiazhuang, China. Sediment samples were collected from cores of boreholes drilled in the vegetable growth plot and the wastewater-irrigated farmland for analyses of nitrogen isotopes, physical and chemical properties, respectively. The profile of borehole A drilled in the vegetable growth plot only applied animal wastes had lower δ¹⁵N values of mean +7.5 ‰ in the upper vadose zone, but higher values of mean +10.9 ‰ in the lower vadose zone. δ¹⁵N values in each part varied little with depth, indicating no or little denitrification occurred in the deep vadose zone below the soil zone. The profile of borehole B drilled in the wastewater-irrigated farmland had low δ¹⁵N values of mean +5.7 ‰ below the soil zone and little variations of δ¹⁵N values with depth, indicating no or little denitrification occurred in the deep vadose zone below the soil zone. This was also verified by consistent variations of NO₃ ^? and SO₄ ^2? contents with Cl^? contents. Our results suggested most of leachable nitrate from the soil zone was hardly subjected to biological attenuation into groundwater.     

Assessing nitrate origin in a volcanic aquifer using a dual isotope approach

Identifying the origin of nitrate is important for the control and management of groundwater quality in aquifer systems. In the southern Apennines (Italy), the Mount Vulture volcanic aquifer is a large and valuable resource of potable and mineral water supply. Unfortunately, signs of anthropogenic impact, especially nitrogen contamination, have recently become evident. In this study, and for the first time, stable isotope ratios (δ¹⁵N and δ¹⁸O) of NO₃ ^? were determined in groundwater to identify their origins and evaluate the presence of transformation processes. The Mount Vulture groundwaters are meteoric in origin, as demonstrated by measurements of δD and δ¹⁸O, and can be divided into two distinct areas based on their NO₃ ^? content. In the southeastern area, characterized by active agricultural land use, the high NO₃ ^? content and the δ¹⁵N–NO₃ isotopic values are due to anthropogenic contamination (inorganic fertilizer). In groundwaters from the western area, the NO₃ ^? contents below 4 mg/L and the δ¹⁵N–NO₃ values can be associated at organic soil N. Evidence for local denitrification may be assumed in a few groundwater samples of the western area showing relatively heavy δ¹⁵N values and low concentrations of nitrate. Finally, the low measured δ¹⁸O values indicate that nitrification occurred in both investigated areas.     

Nitrogen isotope fractionations during progressive metamorphism: A case study from the Paleozoic Cooma metasedimentary complex, southeastern Australia

The well-studied Paleozoic Cooma metamorphic complex in southeastern Australia is characterized by a uniform siliciclastic protolith, of uniform age, with a continuous range of metamorphic grade from subgreenschist- to upper amphibolite-facies, and migmatite-grade in an annular pattern around the Cooma granodiorite. Those conditions are optimal for investigating variations of N concentrations and δ¹⁵N values during progressive metamorphism. Nitrogen concentrations decrease and δ¹⁵N increases with increasing metamorphic grade (sub-chlorite zone: 120 ppm N, δ¹⁵N = 2.3‰; chlorite zone: 110 ppm N, δ¹⁵N = 3.0‰; biotite and andalusite zone: 85 ppm N, δ¹⁵N = 3.8 ‰; sillimanite and migmatite zones: 40 ppm N, δ¹⁵N = 10.7‰). Covariation of K and N contents is consistent with N substituting for K as NH₄⁺ in micas. Observed trends of increasing δ¹⁵N values with decreasing nitrogen concentrations can be explained by a continuous release of nitrogen depleted in ¹⁵N with progressive metamorphism, which causes an enrichment of ¹⁵N in the residual nitrogen of the rock. Equilibrium models for Rayleigh distillation and batch volatilisation for data of the greenschist and amphibolite facies metasedimentary rocks can be explained by N₂-NH₄⁺ exchange at temperatures of 300-600 °C, whereas observed large fractionations for the upper amphibolite-facies and melt products in the migmatite-grade samples may be interpreted as NH₃-NH₄⁺ exchanges at temperature of 650-730 °C. Lower values in the highest grade zones may also stem in part from input of ¹⁵N-depleted fluids from the granodiorite.The magnitude of isotope fractionation of nitrogen is about 1-2‰ during progressive metamorphism of metasedimentary rocks from sub-chlorite zone to biotite-andalusite zone, which is consistent with previous studies. Consequently, the large spread of δ¹⁵N values in Archean greenschist-facies metasedimentary rocks of −6‰ to 30‰ can be accounted for by variable mixtures of mantle plume-dominated volatiles with a δ¹⁵N of −5‰, and a ¹⁵N-enriched marine sedimentary kerogen component inherited from a CI chondrite veneer having δ¹⁵N of 30‰ to 42‰.     

污灌区地下水硝酸盐污染来源的氮同位素示踪

为了识别石家庄市南部污灌区地下水硝酸盐污染来源, 采集5种潜在污染源和19组地下水样用于化学和氮同位素分析.灌溉污水NH₄+的δ15N值较低(4.0‰), 施化肥土壤和粪堆下土壤NO₃-的δ15N值分别为1.4‰和12.4‰; 仅施厩肥的蔬菜种植区下伏近30 m厚包气带沉积物NO₃-的δ15N分布显示, 来自动物粪便的NO₃-已运移到11.5 m以下包气带, 均值10.9‰; 污水灌溉农田下伏厚层包气带沉积物样品分析结果指示, 土壤层下伏包气带沉积物δ15N值变幅较小, 均值5.7‰.污灌区内除一深井外, 其他水井地下水硝酸盐浓度变化在52.6~124.5 mg/L之间, 均值79.72 mg/L, δ15N值变化在5.3‰~8.3‰之间, 均值7.0‰.污灌区地下水的δ15N值较污灌区土壤层下伏包气带沉积物的δ15N值高, 表明地下水NO₃-除了来自灌溉的污水外, 还有δ15N值更高的其他来源, 这些来源主要是人和动物粪便.利用线性混合模型计算, 污灌区地下水NO₃-来自灌溉的污水, 约占76%, 而来自人和动物粪便的NO₃-约占24%.为控制污灌区地下水NO₃-浓度进一步增长, 不仅要加强污水灌溉管理, 还要加强人和动物粪便的管理.      

Impact of agricultural activity and geologic controls on groundwater quality of the alluvial aquifer of the Guadalquivir River (province of Jaén,Spain): a case study

The alluvial aquifer of the Alto Guadalquivir River is one of the most important shallow aquifers in Jaén, Spain. It is located in the central-eastern part of the province, and its groundwater resources are used mainly for crop irrigation in an agriculture-dominated area. Hydrochemical and water-quality data obtained through a 2-year sampling (2004–2006) and analysis program indicate that nitrate pollution is a serious problem affecting groundwater due to the use of nitrogen (N)-fertilizers in agriculture. During the study, 231 water samples were collected from wells and springs to determine water chemistry and the extent of nitrate pollution. The concentration of nitrate in groundwater ranged from 1.25 to 320.88 mg/l. Considerable seasonal fluctuations in groundwater quality were observed as a consequence of agricultural practices and other factors such as annual rainfall distribution and the Guadalquivir River flow regime. The chemical composition of the water is not only influenced by agricultural practices, but also by interaction with the alluvial sediments. The dissolution of evaporites accounts for part of the Na⁺, K⁺, Cl⁻, SO₄ ²⁻, Mg²⁺, and Ca²⁺, but other processes, such as calcite precipitation and dedolomitization, also contribute to groundwater chemistry.     

Impact of agricultural activity and lithology on groundwater quality in the Merdja area, Tebessa, Algeria

This work presents results of the hydrogeological and hydrochemical studies on groundwater samples from the alluvial aquifer of Merdja in Tébessa, located in the Western part of this town. Its groundwater resources are used mainly for crop irrigation in an agriculture dominated area. Hydrochemical and water quality data obtained through a sampling period (December 2008) and analysis program indicate that nitrate pollution can be a serious problem affecting groundwater due to the use of nitrogen (N) fertilizers in agriculture. The concentration of nitrate in groundwater ranged from 19 to 281 mg/l. Considerable seasonal fluctuations in groundwater quality were observed as a consequence of agricultural practices and other factors such as annual rainfall distribution and the wadi El Kebir flow regime. The chemical composition of the water is not only influenced by agricultural practices, but also by interaction with the alluvial sediments. The dissolution of evaporites accounts for part of the Na⁺, K⁺, Cl^?, SO ₄ ^2? , Mg²⁺, and Ca²⁺, but other processes, such as calcite precipitation and dedolomitization, also contribute to groundwater chemistry.     

Determining the genetic origin of nitrate contamination in aquifers of Northern Gujarat,India

Over the past decades, the Gujarat state of India experienced intensive agricultural and industrial activities, fertilizer consumption and abstraction of groundwater, which in turn has degraded the ground water quality. Protection of aquifers from nitrate pollution is a matter of prime concern for the planners and decision-makers. The present study assessed the spatial and temporal variation of groundwater nitrate levels in areas with different land use/land cover activities for both pre- and post-monsoon period. The pre-monsoon nitrate level (1.6–630.7 mg/L) in groundwater was observed to be higher as compared to the post-monsoon level (2.7–131.7 mg/L), possibly due to insufficient recharge and evaporation induced enrichment of agrichemical salts in groundwater. High HCO₃ ^? (200–1,000 mg/L) as well as SO₄ ^2?/Cl^? (0.111–0.992) in post-monsoon period provides a favourable environment for denitrification, and lower the NO₃ levels during the post-monsoon period. The K vs NO₃ scatter plot suggests a common source of these ions when the concentration is <5 mg/L, the relationships between different pollutants and nitrate also suggest that fertilizers and other sources, such as, animal waste, crop residue, septic tanks and effluents from different food processing units present in the area can be attributed to higher nitrate levels in the groundwater. Appropriate agronomic practices such as application of fertilizers based on calibrated soil tests and proper irrigation with respect to crop can minimize the requirement for inorganic fertilizers, which can bring down the cost of cultivation considerably, and also protect groundwater from further degradation.     

Nitrogen circulation and nitrate in groundwater in an agricultural catchment in Southern India

High contents of nitrate in groundwater, ranging up to 1,500 mg/l, have been found. High concentrations are more common in village wells than in irrigation wells situated in the fields. The losses of nitrogen from the soil zone through deep leaching into the groundwater are small (260 kg N/km²); however, due to a small net infiltration (29 mm/year), the median content in groundwater still approaches the permissible limit of 50 mg/l NO ₃ ^? . In villages about 10–20% of the nitrogen from excreta are leached into the groundwater. Mineralization of soil nitrogen during a dry period, followed by heavy rains, caused extremely high contents of nitrate in groundwater.     

Input of seabird-derived nitrogen into rice-paddy fields near a breeding/roosting colony of the Great Cormorant (Phalacrocorax carbo), and its effects on wild grass

Terrestrial ecosystems near breeding/roosting colonies of piscivorous seabirds can receive a large amount of marine-derived N in the form of bird feces. It has been well demonstrated that N input from seabirds strongly affects plant communities in forests or coastal grasslands. The effects of nutrient input on plant communities in agricultural ecosystems near seabird colonies, however, have rarely been evaluated. This relationship was examined in rice-paddy fields irrigated by a pond system located near a colony of the Great Cormorant Phalacrocorax carbo in Aichi, central Japan. In the present study, spatial variations in N content (N %) and N stable isotope composition (δ¹⁵N) of soils and wild grass species together with the growth height of plants in paddy fields in early spring (fallow period) were examined. Soils had a higher N % and δ¹⁵N values in fields associated with an irrigation pond that had N input from cormorants. The δ¹⁵N values tended to be higher around the inlet of irrigation waters, relative to the outlet. These results indicate that cormorant-derived N was input into the paddy fields via the irrigation systems. Plants growing in soil with higher δ¹⁵N had higher δ¹⁵N in the above-ground part of the plants and had luxurious growth. A positive correlation in plant height and δ¹⁵N of NO₃–N was observed in soil plough horizons.     

东阿水文地质单元地下水硝酸盐污染来源的同位素分析

针对近年来地下水硝酸盐污染日益严重的现象,本文运用氮同位素技术对位于典型农业区的东阿水文地质单元地下水氮污染来源进行了研究,结果表明:浅层地下水监测点的NO3-含量较高,平均含量为27.77 mg·L-1 ,δ15N 为7.8‰~12‰,反映了浅层地下水主要受到生活污水或粪便的污染;深层地下水（岩溶水）中NO3- 含量相对较低,平均含量为12.81 mg·L-1,δ15N为7.2‰~14.3‰,同样指示为生活污水或粪便污染,与补给区人为干扰密切相关。部分监测点地下水质量较差,建议研究区内使用高效的灌溉技术及科学的施肥方式,补给区附近的家禽养殖场可通过修建发酵池和改善饲料配方等方式,从源头上降低地下水硝酸盐的输入量。      

Evaluation of diffuse and preferential flow pathways of infiltrated precipitation and irrigation using oxygen and hydrogen isotopes

Subsurface-water flow pathways in three different land-use areas (non-irrigated grassland, poplar forest, and irrigated arable land) in the central North China Plain were investigated using oxygen (¹⁸O) and hydrogen (²H) isotopes in samples of precipitation, soils, and groundwater. Soil water in the top 10 cm was significantly affected by both evaporation and infiltration. Water at 10–40 cm depth in the grassland and arable land, and 10–60 cm in poplar forest, showed a relatively short residence time, as a substantial proportion of antecedent soil water was mixed with a 92-mm storm infiltration event, whereas below those depths (down to 150 cm), depleted δ¹⁸O spikes suggested that some storm water bypassed the shallow soil layers. Significant differences, in soil-water content and δ¹⁸O values, within a small area, suggested that the proportion of immobile soil water and water flowing in subsurface pathways varies depending on local vegetation cover, soil characteristics and irrigation applications. Soil-water δ¹⁸O values revealed that preferential flow and diffuse flow coexist. Preferential flow was active within the root zone, independent of antecedent soil-water content, in both poplar forest and arable land, whereas diffuse flow was observed in grassland. The depleted δ¹⁸O spikes at 20–50 cm depth in the arable land suggested the infiltration of irrigation water during the dry season. Temporal isotopic variations in precipitation were subdued in the shallow groundwater, suggesting more complete mixing of different input waters in the unsaturated zone before reaching the shallow groundwater.

     

Integration of geochemical and isotopic tracers for elucidating water sources and salinization of shallow aquifers in the sub-Saharan Drâa Basin,Morocco

In the arid sub-Saharan of southern Morocco, groundwater salinization poses a direct threat for agricultural production in six oases’ basins that are irrigated by water imported from the High Atlas Mountains. Here the geospatial distribution of salinity is evaluated in shallow groundwater, springs and surface waters in the Drâa Basin, integrating major and trace element geochemistry and isotopic tracers (O, H, Sr and B). The data show that water discharge from the High Atlas Mountains to the Upper section of the Drâa Basin is characterized by both low and high salinity, a distinctive low δ¹⁸O and δ²H composition (as low as −9‰ and −66‰, respectively), typical for meteoric water from high elevation, a ⁸⁷Sr/⁸⁶Sr range of 0.7078–0.7094, and δ¹¹B of 12–17‰. The Ca–Mg–HCO₃, Na–Cl–SO₄, and Ca–SO₄ compositions as well as the Br/Cl, ⁸⁷Sr/⁸⁶Sr, and δ¹¹B values of the saline water suggest dissolution of Lower Jurassic carbonates and evaporite rocks in the High Atlas Mountain catchment. Storage and evaporation of the imported water in a man-made open reservoir causes an enrichment of the stable isotope ratios with a δ¹⁸O/δ²H slope of <8 but no change in the Sr and B isotope fingerprints. Downstream from the reservoir, large salinity variations were documented in the shallow groundwater from the six Drâa oases, with systematically higher salinity in the three southern oases, up to 12,000 mg/L. The increase of the salinity is systematically associated with a decrease of the Br/Cl ratio, indicating that the main mechanism of groundwater salinization in the shallow aquifers in the Drâa oases is via salt dissolution (gypsum, halite) in the unsaturated zone. Investigation of shallow groundwater that flows to the northern Drâa oases revealed lower salinity (TDS of 500–4225) water that is characterized by depleted ¹⁸O and ²H (as low as −9‰ and −66‰, respectively) and higher ⁸⁷Sr/⁸⁶Sr ratios (∼0.7107–0.7115) relative to irrigation water and groundwater flow from the Upper Drâa Basin. This newly-discovered low-saline groundwater with a different isotopic imprint flows from the northeastern Anti-Atlas Jabel Saghro Mountains to the northern oases of the Lower Drâa Basin. This adjacent subsurface flow results in a wide range of Sr isotope ratios in the shallow oases groundwater (0.7084–0.7131) and appears to mitigate salinization in the three northern Drâa oases. In contrast, in the southern oases, the higher salinity suggests that this mitigation is not as affective and increasing salinization through cycles of water irrigation and salt dissolution appears inevitable.     

Contribution of {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} and 13CTDIC Evaluation to the Identification of CO2 Sources in Volcanic Groundwater Systems: Influence of Hydrometeorological Conditions and Lava Flow Morphologies—Application to the Argnat Basin (Chaîne des Puys, Massif Central, France)

Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO₂ whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC (total dissolved inorganic carbon) on various spatiotemporal scales in the unsaturated and saturated zones of volcanic flows of the Argnat basin (French Massif Central) have been carried out to identify the carbon sources in the system. Mantellic sources are related to faults promoting CO₂ uplift from the mantle to the saturated zone. The contribution of this source is counterbalanced by infiltration of water through the unsaturated zone, accompanied by dissolution of soil CO₂ or even atmospheric CO₂ during cold periods. Monitoring and modeling of δ¹³C_TDIC in the unsaturated zone shows that both $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC are controlled by air temperature which influences soil respiration and soil-atmosphere CO₂ exchanges. The internal geometry of volcanic lava flows controls water patterns from the unsaturated zone to saturated zone and thus may explain δ¹³C heterogeneity in the saturated zone at the basin scale.     

Open to closed system transition traced through the TDIC isotopic signature at the aquifer recharge stage, implications for groundwater C dating

¹⁴C dating models are limited when considering recent groundwater for which the carbon isotopic signature of the total dissolved inorganic carbon (TDIC) is mainly acquired in the unsaturated zone. Reducing the uncertainties of dating thus implies a better identification of the processes controlling the carbon isotopic composition of the TDIC during groundwater recharge. Geochemical interactions between gas, water and carbonates in the unsaturated zone were investigated for two aquifers (the carbonate-free Fontainebleau sands and carbonate-bearing Astian sands, France) in order to identify the respective roles of CO₂ and carbonates on the carbon isotopic signatures of the TDIC; this analysis is usually approached using open or closed system terms. Under fully open system conditions, the seasonality of the ¹³C values in the soil CO₂ can lead to important uncertainties regarding the so-called “initial ¹⁴C activity” used in ¹⁴C correction models. In a carbonate-bearing unsaturated zone such as in the Astian aquifer, we show that an approach based on fully open or closed system conditions is not appropriate. Although the chemical saturation between water and calcite occurs rapidly within the first metre of the unsaturated zone, the carbon isotopic contents (δ¹³C) of the CO₂ and the TDIC evolve downward, impacted by the dissolution-precipitation of the carbonates. In this study, we propose a numerical approach to describe this evolution. The δ¹³C and the A¹⁴C (radiocarbon activity) of the TDIC at the base of the carbonate-bearing unsaturated zone depends on (i) the δ¹³C and the A¹⁴C of the TDIC in the soil determined by the soil CO_2, (ii) the water’s residence time in the unsaturated zone and (iii) the carbonate precipitation-dissolution fluxes. In this type of situation, the carbonate δ¹³C-A¹⁴C evolutions indicate the presence of secondary calcite and permit the calculation of its accretion flux, equal to . More generally, for other sites under temperate climate and with similar properties to the Astian sands site, this approach allows for a reliable determination of the carbon isotopic composition at the base of the unsaturated zone as the indispensable “input function” data of the carbon cycle into the aquifer.     

Identification of sulfate sources in groundwater using isotope analysis and modeling of flood irrigation with waters of different quality in the Jinghuiqu district of China

The main objective of this study was to identify the main sources and processes that control SO₄ ^2? groundwater concentrations in the Jinghuiqu irrigation district of China using isotope analysis. Lysimeter irrigation experiments and numerical modeling were used to assess the impact of long-term irrigation practices on sulfate transport, when different sources of irrigation water were used. SO₄ ^2? concentrations in the groundwater of the entire irrigation area increased significantly from the years 1990 (a mean value was 4.8 mmol L^?1) to 2009 (a mean value was 9.84 mmol L^?1). The δ³⁴S-SO₄ ^2? values (ranging from +5.27 to +10.69 ‰) indicated that sulfates in groundwater were initially predominantly derived from dissolution of minerals. However, no soluble sulfate minerals (gypsum and/or mirabilite) were detected after 1990. To better understand this seeming anomaly, water content and SO₄ ^2? data were collected before and after the field irrigation experiment and analyzed using the HYDRUS-1D and HP1 software packages. The experimental data were also used to assess sulfate leaching when different sources of irrigation water were used under current irrigation practices. The dissolved sulfate concentrations in the soil profile increased significantly when groundwater was used for infiltration compared to the use of surface water. Irrigation water sources had a great impact on the increase of sulfate concentrations in the shallow groundwater, especially when groundwater with elevated concentrations was used for irrigation.     

湖北泉水河流域水化学特征和硝酸盐来源示踪

目前针对喀斯特山区及平原过渡带天然河流硝酸盐的来源识别与追踪的研究鲜有报道,也较少考虑湿润气候区反季节性干旱气候特征对硝酸盐迁移规律的影响.以汉江二级支流泉水河流域为例,分析了从源头喀斯特地区、中间过渡区、平原区地表水和地下水硝酸盐含量及组成的空间变化,采用氮氧同位素识别地表水和地下水硝酸盐来源,利用SIAR模型定量计算各污染源的贡献率.结果表明:土壤有机氮、污水粪便、化肥和大气沉降对地下水硝酸盐来源贡献占比分别为31.4%、20.0%、29.6%和19.0%,对地表水硝酸盐来源的比例分别为32.0%、30.0%、25.0%和13.0%,污水粪便对地表水硝酸盐贡献比例较地下水增高;坝上水样因水体较大,自净能力较强,受污水粪便的影响很小（仅为9.0%）,坝上水样硝酸盐土壤有机氮、大气沉降和化肥的贡献占比分别为43.0%、11.0%和37.0%.枯水期河水主要由地下水缓慢补给,无地表径流汇入,土壤有机氮为河流主要的硝酸盐来源,河流中下游更易受人类活动影响,生活污水和化肥对河流硝酸盐贡献增大.      

Environmental isotopic study on the recharge and residence time of groundwater in the Heihe River Basin, northwestern China

The recharge and origin of groundwater and its residence time were studied using environmental isotopic measurements in samples from the Heihe River Basin, China. δ¹⁸O and δD values of both river water and groundwater were within the same ranges as those found in the alluvial fan zone, and lay slightly above the local meteoric water line (δD=6.87δ¹⁸O+3.54). This finding indicated that mountain rivers substantially and rapidly contribute to the water resources in the southern and northern sub-basins. δ¹⁸O and δD values of groundwater in the unconfined aquifers of these sub-basins were close to each other. There was evidence of enrichment of heavy isotopes in groundwater due to evaporation. The most pronounced increase in the δ¹⁸O value occurred in agricultural areas, reflecting the admixture of irrigation return flow. Tritium results in groundwater samples from the unconfined aquifers gave evidence for ongoing recharge, with mean residence times of: less than 36 years in the alluvial fan zone; about 12–16 years in agricultural areas; and about 26 years in the Ejina oasis. In contrast, groundwater in the confined aquifers had ¹⁴C ages between 0 and 10 ka BP.     

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.     

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.