Geochemistry and origin of inorganic contaminants in soil, river sediment and surface water in a heavily urbanized river basin.

Understanding the geochemistry and contamination of rivers affected by anthropogenic activities is paramount to water resources management. The Asopos river basin in central Greece is facing environmental quality deterioration threats due to industrial, urban and agricultural activities. Here, the geochemistry of river sediments and adjacent soil in terms of major and trace elements (Al, Ca, Mg, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and the geochemical composition of surface water in terms of major ions, trace elements and nutrients along the Asopos river basin were determined. In addition, this study characterized potential nitrate sources through the analysis of stable isotope composition of NO3- (δ15Ν-ΝΟ3- and δ18Ο-ΝΟ3-). Results indicated that specific chemical constituents including nutrients (NO2-, NH4+, PO43-) and major ions (Na+, Cl-) were highest in the urban, industrialized and downstream areas. On the other hand, nitrate (NO3-) concentration in river water (median 7.9 mg/L) showed a decreasing trend from the upstream agricultural sites to the urban area and even more in the downstream of the urban area sites. Ionic ratios (NO3-/Cl-) and δ15Ν-ΝΟ3- values (range from +10.2 ‰ to +15.7 ‰), complemented with a Bayesian isotope mixing model, clearly showed the influence of organic wastes from septic systems and industries operating in the urban area on river nitrate geochemistry. The interpretation of geochemical data of soil and river sediment samples demonstrated the strong influence of local geology on Cr, Fe, Mn and Ni content, with isolated samples showing elevated concentrations of Cd, Cu, Pb and Zn, mostly within the industrialized urban environment. The calculation of enrichment factors based on the national background concentrations provided limited insights into the origin of geogenic metals. Overall, this study highlighted the need for a more holistic approach to assess the impact of the geological background and anthropogenic activities on river waters and sediments.

Stable isotopes reveal organic nitrogen pollution and cycling from point and non-point sources in a heavily cultivated (agricultural) Mediterranean river basin.

The Pinios River Basin (PRB) is the most intensively cultivated area in Greece, which hosts numerous industries and other anthropogenic activities. The analysis of water samples collected monthly for ∼1 ½ years in eight monitoring sites in the PRB revealed nitrate pollution of organic origin extending from upstream to downstream and occurring throughout the year, masking the signal from the application of synthetic fertilizers. Nitrate concentrations reached up to 3.6 mg/l as NO3--N, without exceeding the drinking water threshold of ∼11.0 mg/l (as NO3--N). However, the water quality status was "poor" or "bad" in ∼50 % of the samples based on a local index, which considers the potential impact of nitrate on aquatic biological communities. The δ15Ν-ΝΟ3- and δ18O-NO3- values ranged from +4.4 ‰ to +20.3 ‰ and from -0.5 ‰ to +14.4 ‰, respectively. The application of a Bayesian model showed that the proportional contribution of organic pollution from industries, animal breeding facilities and manure fertilizers exceeded 70 % in most river sites with an overall uncertainty of ∼0.3 (UI90 index). The δ18O-NO3- and its relationship with δ18O-H2O revealed N-cycling and mixing processes, which were difficult to identify apart from the uptake of nutrients by phytoplankton during the growing season and metabolic activities. The strong correlation of δ15Ν-ΝΟ3- values with a Land Use Index (LUI) and a Point Source Index (PSI) highlighted not only the role of non-point nitrate sources but also of point sources of nitrate pollution on water quality degradation, which are usually overlooked. The nitrification of organic wastes is the dominant nitrate source in most rivers in Europe. The systematic monitoring of rivers for nitrate isotopes will help improve the understanding of N-cycling and the impact of these pollutants on ecosystems and better inform policies for protection measures so to achieve good ecological status.

Sources of major elements and nutrients in the water cycle of an undisturbed river basin - Samothraki Island, Greece.

We studied the origin of elements of an undisturbed stream basin during the dry season as derived by atmospheric inputs and lithological processes. Α mass balance model was applied taking into account atmospheric (rain and vapor) inputs and their origin from marine aerosol and dust, as well as the contribution of rock mineral weathering and dissolution of soluble salts. The model results were enhanced using element enrichment factors, element ratios and water stable isotopes. Weathering and dissolution of bedrock and soil minerals contributed the main element portions, besides sodium and sulfate that chiefly derived from wet deposition. Vapor was shown to contribute water to inland waters of the basin. However, rain was the main source of elements compared to vapor, with marine aerosol being the only atmospheric chloride source, contributing also over 60 % of atmospheric sodium and magnesium. Silicate derived from mineral weathering (mainly plagioclase and amorphous silica), while soluble salt dissolution contributed the main portions of the rest of major elements. In headwater springs and streams, element concentrations were more affected by atmospheric inputs and silicate mineral weathering was more intense, contrary to lowland waters that were more affected by soluble salt dissolution. Effective self-purification processes were mirrored in low nutrient levels, despite the significant inputs from wet deposition, with rain being more important contributor than vapor for the majority of nutrient species. Relatively high nitrate concentrations in headwaters were attributed to increased mineralization and nitrification, while the downstream nitrate diminishing was due to prevailing denitrification processes. The ultimate goal of this study is to contribute in establishing stream elements' reference conditions using mass balance modeling approaches.

Nitrate isotopes (δ15N, δ18O) in precipitation: best practices from an international coordinated research project.

Stable isotope ratios of nitrogen and oxygen (15N/14N and 18O/16O) of nitrate (NO3-) are excellent tracers for developing systematic understanding of sources, conversions, and deposition of reactive atmospheric nitrogen (Nr) in the environment. Despite recent analytical advances, standardized sampling of NO3-) isotopes in precipitation is still lacking. To advance atmospheric studies on Nr species, we propose best-practice guidelines for accurate and precise sampling and analysis of NO3- isotopes in precipitation based on the experience obtained from an international research project coordinated by the International Atomic Energy Agency (IAEA). The precipitation sampling and preservation strategies yielded a good agreement between the NO3- concentrations measured at the laboratories of 16 countries and at the IAEA. Compared to conventional methods (e.g., bacterial denitrification), we confirmed the accurate performance of the lower cost Ti(III) reduction method for isotope analyses (15N and 18O) of NO3- in precipitation samples. These isotopic data depict different origins and oxidation pathways of inorganic nitrogen. This work emphasized the capability of NO3- isotopes to assess the origin and atmospheric oxidation of Nr and outlined a pathway to improve laboratory capability and expertise at a global scale. The incorporation of other isotopes like 17O in Nr is recommended in future studies.

Nitrate isotopes reveal N-cycled waters in a spring-fed agricultural catchment.

Nitrate stable isotopes provide information about nitrate contamination and cycling by microbial processes. The Fischa-Dagnitz (Austria) spring and river system in the agricultural catchment of the Vienna basin shows minor annual variance in nitrate concentrations. We measured nitrate isotopes (δ15N, δ18O) in the source spring and river up to the confluence with the Danube River (2019-2020) with chemical and water isotopes to assess mixing and nitrate transformation processes. The Fischa-Dagnitz spring showed almost stable nitrate concentration (3.3 ± 1.0 mg/l as NO3--N) year-round but surprisingly variable δ15N, δ18O-NO3- values ranging from +5.5 to +11.1‰ and from +0.5 to +8.1‰, respectively. The higher nitrate isotope values in summer were attributed to release of older denitrified water from the spring whose isotope signal was dampened downstream by mixing. A mixing model suggested denitrified groundwater contributed > 50 % of spring discharge at baseflow conditions. The isotopic composition of NO3- in the gaining streams was partly controlled by nitrification during autumn and winter months and assimilation during the growing season resulting in low and high δ15N-NO3- values, respectively. NO3- isotope variation helped disentangle denitrified groundwater inputs and biochemical cycling processes despite minor variation of NO3- concentration.

Assessment of natural and anthropogenic contamination sources in a Mediterranean aquifer by combining hydrochemical and stable isotope techniques.

The Atalanti basin is an intensively cultivated area in central Greece, facing groundwater quality deterioration threats due to natural and anthropogenic-related contamination sources. A combination of statistical and hydrogeochemical techniques, and stable isotope compositions (δ2H-H2O and δ18Ο-Η2Ο, δ15Ν-ΝΟ3- and δ18Ο-ΝΟ3-, δ34S-SO42- and δ18O-SO42-) were applied to elucidate the origin of salinity and nitrate contamination, and shed light on the potential associations between geogenic Cr(VI) and NO3- sources and transformations. Nitrate and Cr(VI) concentrations reached up to 337 mg L-1 and 76.1 µg L-1, respectively, exceeding WHO threshold values in places. The cluster of samples with the high salinity was mostly influenced by irrigation return flow and marine aerosols, and less by seawater intrusion, as evidenced by the ionic ratios (e.g., Na+/Cl-) and the stable isotopes of oxygen and hydrogen in water, and sulphur and oxygen in sulphates. The δ15Ν-ΝΟ3- and δ18O-NO3- values ranged from +2.0 ‰ to +14.5 ‰ and + 0.3 ‰ to +11.0 ‰, respectively. We found that the dominant sources of NO3- in groundwater were fertilizers in the central part of the area and sewage waste in the northern part around the residential area of Livanates. The occurrence of denitrification was evident in the northern part of the basin, where the DO levels were lowest (≤ 2.2 mg L-1), whereas nitrification of NH4+-fertilizers prevailed in the central part. Elevated Cr(VI) values (≥ 20 µg/l) were associated with the lowest deviation of the measured from the theoretical nitrification δ18Ο-NO3- values, whereas the lowest Cr(VI) values were observed in the denitrified water samples. Our isotope findings revealed the strong influence of redox conditions on the biogeochemical transformations of N species and the mobilization of Cr(VI) that will help improve the understanding of the fate of these contaminants from the unsaturated zone to the groundwater in areas of agricultural and urban land use.

Stable isotopes in global lakes integrate catchment and climatic controls on evaporation.

Global warming is considered a major threat to Earth's lakes water budgets and quality. However, flow regulation, over-exploitation, lack of hydrological data, and disparate evaluation methods hamper comparative global estimates of lake vulnerability to evaporation. We have analyzed the stable isotope composition of 1257 global lakes and we find that most lakes depend on precipitation and groundwater recharge subsequently altered by catchment and lake evaporation processes. Isotope mass-balance modeling shows that ca. 20% of water inflow in global lakes is lost through evaporation and ca. 10% of lakes in arid and temperate zones experience extreme evaporative losses >40 % of the total inflow. Precipitation amount, limnicity, wind speed, relative humidity, and solar radiation are predominant controls on lake isotope composition and evaporation, regardless of the climatic zone. The promotion of systematic global isotopic monitoring of Earth's lakes provides a direct and comparative approach to detect the impacts of climatic and catchment-scale changes on water-balance and evaporation trends.

Stable isotopic characterization of nitrate wet deposition in the tropical urban atmosphere of Costa Rica.

Increasing energy consumption and food production worldwide results in anthropogenic emissions of reactive nitrogen into the atmosphere. To date, however, little information is available on tropical urban environments where inorganic nitrogen is vastly transported and deposited through precipitation on terrestrial and aquatic ecosystems. To fill this gap, we present compositions of water stable isotopes in precipitation and atmospheric nitrate (δ18O-H2O, δ2H-H2O, δ15N-NO3-, and δ18O-NO3-) collected daily between August 2018 and November 2019 in a tropical urban atmosphere of central Costa Rica. Rainfall generation processes (convective and stratiform rainfall fractions) were identified using stable isotopes in precipitation coupled with air mass back trajectory analysis. A Bayesian isotope mixing model using δ15N-NO3- compositions and corrected for potential 15N fractionation effects revealed the contribution of lightning (25.9 ± 7.1%), biomass burning (21.8 ± 6.6%), gasoline (19.1 ± 6.4%), diesel (18.4 ± 6.0%), and soil biogenic emissions (15.0 ± 2.6%) to nitrate wet deposition. δ18O-NO3- values reflect the oxidation of NOx sources via the ·OH + RO2 pathways. These findings provide necessary baseline information about the combination of water and nitrogen stable isotopes with atmospheric chemistry and hydrometeorological techniques to better understand wet deposition processes and to characterize the origin and magnitude of inorganic nitrogen loadings in tropical regions.

Comparative evaluation of urban versus agricultural nitrate sources and sinks in an unconfined aquifer by isotopic and multivariate analyses.

Nitrate (NO3-) is one of the most widespread contaminants in groundwater primarily due to agricultural activities utilizing N-containing fertilizers and the presence of animal wastes. Hydrochemical and nitrate isotope data (δ15N-NO3- and δ18O-NO3-) from the unconfined aquifer in the urban area of Del Campillo city and its surrounding rural area with different land-use types, i.e. individual sanitation systems, agricultural areas and livestock breeding facilities, were generated to investigate the impact of nitrogen pollution sources and to assess N-biogeochemical processes. The Principal Component Analysis of hydrochemical and isotopic data were used to compare the factors that control the groundwater quality and particularly the nitrate concentrations in the urban and the rural area. The results showed that nitrate pollution in the urban area of Del Campillo city originated mainly from the on-site sanitation systems and/or animal domestic wastes, whereas in the rural area nitrate pollution was mostly attributed to a combination of urea-based fertilizers and manure from livestock breeding activities. The aquifer is under oxic to suboxic conditions in the rural area and becomes suboxic in the urban area where the higher supply of organic matter consumes oxygen. As a result, denitrification was more significant in the urban area compared to the rural area, as evidenced by the higher N and O isotope enrichment factor (ε). This work will be used to benchmark the current nitrate contamination status in the region and evaluate effective planning of environmental measures and remediation strategies.

Application of isotope techniques to enhance the conceptual hydrogeological model and to assess groundwater sustainability in the Pampean plain in Córdoba, Argentina.

The objective of this work is to enhance the conceptual hydrogeological model in the Río Cuarto River basin by using isotope and hydrochemical techniques. The precipitation pattern, as reflected in the average values of δ 2H and δ 18O in stations located in the plains and in the mountains, showed an isotope depletion from the East to the West, attributed to continental and altitude effects. Groundwater quality is mainly the result of two controlling factors: lithology and flow distances from recharge. The aquifers show fresh calcium/sodium bicarbonate water in the upper and medium basin (coarse fluvial sediments) which evolve to sodium sulphate and chloride waters in the low basin (mainly loess and fine alluvial sediments). The confined aquifer systems in the lower basin (C and D systems) averaged more negative stable isotope values, indicating that groundwater recharged during colder climatic conditions (Pleistocene period). Groundwater dating with 14C confirmed that groundwater ages range from modern to 45,000 years BP showing that as the water flows towards deeper layers and farther from the mountainous recharge area, groundwater age increases. The confined aquifers can potentially be exploited in order to partly cover different water needs but they should be managed in a sustainable way.

Origin, implications and management strategies for nitrate pollution in surface and ground waters of Anthemountas basin based on a δ15N-NO3- and δ18O-NO3- isotope approach.

Nitrate pollution of surface and groundwater resources is a major worldwide environmental problem. In this study nitrogen isotopes of water, soil, fertilizer and manure were analyzed to determine the pollution sources of nitrate in the groundwater and surface waters of Anthemountas basin. The SIAR model and multivariate statistical analysis were used to determine and quantify the contribution of different NO3̄ sources in groundwater and surface water. Additionally, a detailed literature overview was carried out to identify the origin of nitrate pollution in surface and ground waters based on ΝΟ3- isotopes. The Piper diagram identified the dominant water types as Mg-Ca-HCO3 and Ca-Mg-HCO3. Nitrate concentrations reached 162.0 mg/L in groundwater and 39.0 mg/L in surface waters. The main source of nitrate in groundwater was mainly nitrified ammonium-based synthetic urea and less nitrate-based synthetic fertilizers. The correlation of SIAR results with other trace elements revealed a negative correlation between hexavalent chromium and a) nitrate-based synthetic fertilizers, and b) nitrification of urea synthetic fertilizers. However, a positive correlation was observed between hexavalent chromium and anthropogenic organic matter. The literature overview provided the basis to design a novel management protocol for nitrate pollution that includes three steps: a) fundamental research, b) management tools, c) monitoring and preservation actions. However, an integrated management protocol for nitrate pollution requires a deeper understanding of the hydro-system and the full participation of local farmers and stakeholders.

Application of isotope techniques to study groundwater resources in the unconsolidated aquifers along the Ping River (Thailand).

Severe droughts during the dry season and floodings during the rainy season are among the major problems encountered in the valleys along the Ping River in Thailand. Improving our understanding of the groundwater resources in this agricultural area is an important issue for the sustainable development of the region. Hence, in order to gain understanding on the groundwater flow dynamics in the unconsolidated shallow aquifers along the Ping River, stable (13C, 18O, 2H, noble gases) and radioactive (3H, 14C) isotope techniques were combined with hydrogeochemical tools. The comprehensive interpretation of the chemical and isotope data consistently showed different origins for groundwater in the northern and southern areas of the investigated aquifers. Groundwaters in the northern part have younger 3H/3He ages, are less mineralized, and have suffered a stronger evaporation than groundwaters in the southern part of the aquifer. Overall, our results are consistent with the hydrogeological situation of the investigated area, namely shallow groundwaters and a spatially extended recharge. 3H/3He apparent ages indicated that young groundwater (<50 years) is present in all the investigated wells. Elevated concentrations of some pollutants (nitrate and phosphate) in parts of the aquifer evidenced a relatively high vulnerability of the aquifer to surface pollution.

A biological and nitrate isotopic assessment framework to understand eutrophication in aquatic ecosystems.

Eutrophication is a globally significant challenge facing aquatic ecosystems, mostly associated with human induced enrichment of these ecosystems with nitrogen and phosphorus. Given the complexity of assigning eutrophication issues to local primary N sources in field-based studies, this paper proposes a multi-stable isotope and biological framework to track nitrogen biogeochemical transformations, inputs and fate of nitrate in groundwater-dependent shallow lakes. Three representative freshwater ecosystems from the Pampa Plain (Argentina), with different land uses and topographic features were selected. Groundwater (N = 24), lake (N = 29) and stream (N = 20) samples were collected for isotope (δ15N-NO3- and δ18O-NO3-, δ18O-H2O) and hydrogeochemical (major ions and nutrients) determinations, and in the case of surface water, also for biological determinations (chlorophyll-a, fecal coliforms and nitrifying bacteria abundance). Both chemical and isotopic characteristics clearly indicated that denitrification was limited in lakes and streams, while evidence of assimilation in shallow lakes was confirmed. The results suggested that groundwater denitrification plays a role in the nitrate concentration pattern observed in the Pampeano Aquifer. The proportional contribution of nitrate sources to the inflow streams for all years were estimated by using Bayesian isotope mixing models, being ammonium nitrified in the system from soil and fertilizers ~50 - 75 %, sewage/manure ~20 - 40 % and atmospheric deposition ~5 - 15 %. In this sense, agricultural practices seem to have a relevant role in the eutrophication and water quality deterioration for these watersheds. However, limnological, bacterial and algal variables, assessed simultaneously with isotopic tracers, indicated spatio-temporal differences within and between these aquatic ecosystems. In the case of Nahuel Rucá Lake, animal manure was a significant source of nitrogen pollution, in contrast to La Brava Lake. In Los Padres Lake, agricultural practices were considered the main sources of nitrate input to the ecosystem.

Nitrate source identification in groundwater of multiple land-use areas by combining isotopes and multivariate statistical analysis: A case study of Asopos basin (Central Greece).

Nitrate (NO3) is one of the most common contaminants in aquatic environments and groundwater. Nitrate concentrations and environmental isotope data (δ(15)N-NO3 and δ(18)O-NO3) from groundwater of Asopos basin, which has different land-use types, i.e., a large number of industries (e.g., textile, metal processing, food, fertilizers, paint), urban and agricultural areas and livestock breeding facilities, were analyzed to identify the nitrate sources of water contamination and N-biogeochemical transformations. A Bayesian isotope mixing model (SIAR) and multivariate statistical analysis of hydrochemical data were used to estimate the proportional contribution of different NO3 sources and to identify the dominant factors controlling the nitrate content of the groundwater in the region. The comparison of SIAR and Principal Component Analysis showed that wastes originating from urban and industrial zones of the basin are mainly responsible for nitrate contamination of groundwater in these areas. Agricultural fertilizers and manure likely contribute to groundwater contamination away from urban fabric and industrial land-use areas. Soil contribution to nitrate contamination due to organic matter is higher in the south-western part of the area far from the industries and the urban settlements. The present study aims to highlight the use of environmental isotopes combined with multivariate statistical analysis in locating sources of nitrate contamination in groundwater leading to a more effective planning of environmental measures and remediation strategies in river basins and water bodies as defined by the European Water Frame Directive (Directive 2000/60/EC).

Multivariate statistical analysis of the hydrogeochemical and isotopic composition of the groundwater resources in northeastern Peloponnesus (Greece).

The present study involves an integration of the hydrogeological, hydrochemical and isotopic (both stable and radiogenic) data of the groundwater samples taken from aquifers occurring in the region of northeastern Peloponnesus. Special emphasis has been given to health-related ions and isotopes in relation to the WHO and USEPA guidelines, to highlight the concentrations of compounds (e.g., As and Ba) exceeding the drinking water thresholds. Multivariate statistical analyses, i.e. two principal component analyses (PCA) and one discriminant analysis (DA), combined with conventional hydrochemical methodologies, were applied, with the aim to interpret the spatial variations in the groundwater quality and to identify the main hydrogeochemical factors and human activities responsible for the high ion concentrations and isotopic content in the groundwater analysed. The first PCA resulted in a three component model, which explained approximately 82% of the total variance of the data sets and enabled the identification of the hydrogeological processes responsible for the isotopic content i.e., δ(18)Ο, tritium and (222)Rn. The second PCA, involving the trace element presence in the water samples, revealed a four component model, which explained approximately 89% of the total variance of the data sets, giving more insight into the geochemical and anthropogenic controls on the groundwater composition (e.g., water-rock interaction, hydrothermal activity and agricultural activities). Using discriminant analysis, a four parameter (δ(18)O, (Ca+Mg)/(HCO3+SO4), EC and Cl) discriminant function concerning the (222)Rn content was derived, which favoured a classification of the samples according to the concentration of (222)Rn as (222)Rn-safe (<11 Bq·L(-1)) and (222)Rn-contaminated (>11 Bq·L(-1)). The selection of radon builds on the fact that this radiogenic isotope has been generally related to increased health risk when consumed.

Application of stable isotopes and hydrochemical analysis in groundwater aquifers of Argolis Peninsula (Greece).

The present study examines the isotopic and hydrochemical composition of 18 inland spring waters and 3 coastal karstic spring waters, covering the period between October 2005 and March 2008. The stable isotopes ((18)O, (2)H) processing has revealed the absence of significant evaporation phenomena and that the origin of fresh water samples is meteoric. Using (18)O values in rainfall waters, an average line of isotopic depletion with altitude has been constructed, extracting a rate of-0.45‰/100 m as typical for the study area. Furthermore, the mean altitude of recharge of the springs has been estimated by plotting the groundwater sampling points on a δ(18)O versus altitude diagram. Hydrochemistry results have shown that the dissolution of carbonate, flysch and ophiolitic formations defines the hydrochemical characteristics of groundwater. Moreover, seawater intrusion in the coastal area is significantly high, causing the water in the three karstic springs to be brackish.