Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China

Nitrate (NO<sub>3</sub><sup>−</sup>) pollution resulting from anthropogenic activities represents one of the most prevalent environmental issues in karst spring catchments of northern China. In June 2021, a comprehensive study was conducted in the Jinan Spring Catchment (JSC)...

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Main Authors: Kairan Wang, Mingyuan Fan, Zhen Wu, Xin Zhang, Hongbo Wang, Xuequn Chen, Mingsen Wang
Format: Article
Language:English
Published: MDPI AG 2025-05-01
Series:Toxics
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Online Access:https://www.mdpi.com/2305-6304/13/5/393
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author Kairan Wang
Mingyuan Fan
Zhen Wu
Xin Zhang
Hongbo Wang
Xuequn Chen
Mingsen Wang
author_facet Kairan Wang
Mingyuan Fan
Zhen Wu
Xin Zhang
Hongbo Wang
Xuequn Chen
Mingsen Wang
author_sort Kairan Wang
collection DOAJ
description Nitrate (NO<sub>3</sub><sup>−</sup>) pollution resulting from anthropogenic activities represents one of the most prevalent environmental issues in karst spring catchments of northern China. In June 2021, a comprehensive study was conducted in the Jinan Spring Catchment (JSC), where 30 groundwater and surface water samples were collected. The sources and spatial distribution of nitrate pollution were systematically investigated through hydrochemical analysis combined with dual-isotope tracing techniques (δ<sup>15</sup>N<sub>NO3</sub> and δ<sup>18</sup>O<sub>NO3</sub>). Analytical results revealed that the predominant anion and cation sequences were HCO<sub>3</sub><sup>−</sup> > SO<sub>4</sub><sup>2−</sup> > Cl<sup>−</sup> > NO<sub>3</sub><sup>−</sup> and Ca<sup>2+</sup> > Na<sup>+</sup> > Mg<sup>2+</sup> > K<sup>+</sup>, respectively, with HCO<sub>3</sub>·SO<sub>4</sub>-Ca identified as the primary hydrochemical type. Notably, the average NO<sub>3</sub><sup>−</sup> concentration in groundwater (46.62 mg/L) significantly exceeded that in surface water (4.96 mg/L). Among the water samples, 11 locations exhibited substantial nitrate pollution, demonstrating an exceedance rate of 42%. Particularly, the NO<sub>3</sub><sup>−</sup>-N concentrations in both the upstream recharge area and downstream drainage area were markedly higher than those in the runoff area. The spatial distribution of NO<sub>3</sub><sup>−</sup> concentrations was primarily influenced by mixing processes, with no significant evidence of denitrification observed. The isotopic compositions ranged from −1.42‰ to 12.79‰ for δ<sup>15</sup>N<sub>NO3</sub> and 0.50‰ to 15.63‰ for δ<sup>18</sup>O<sub>NO3</sub>. Bayesian isotope mixing model (MixSIAR) analysis indicated that domestic sewage and manure constituted the principal nitrate sources, contributing 37.1% and 56.9% to groundwater and surface water, respectively. Secondary sources included soil organic nitrogen, rainfall and fertilizer NH<sub>4</sub><sup>+</sup>, and chemical fertilizers, while atmospheric deposition showed the lowest contribution rate. Additionally, potential mixing of soil organic nitrogen with chemical fertilizer was identified.
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spelling doaj-art-7b97708fbba144fdaa0ecefe221de51d2025-08-20T01:56:45ZengMDPI AGToxics2305-63042025-05-0113539310.3390/toxics13050393Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, ChinaKairan Wang0Mingyuan Fan1Zhen Wu2Xin Zhang3Hongbo Wang4Xuequn Chen5Mingsen Wang6Water Resources Research Institute of Shandong Province, Jinan 250014, ChinaWater Resources Research Institute of Shandong Province, Jinan 250014, ChinaWater Resources Research Institute of Shandong Province, Jinan 250014, ChinaWater Resources Research Institute of Shandong Province, Jinan 250014, ChinaSchool of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan 250101, ChinaWater Resources Research Institute of Shandong Province, Jinan 250014, ChinaWater Resources Research Institute of Shandong Province, Jinan 250014, ChinaNitrate (NO<sub>3</sub><sup>−</sup>) pollution resulting from anthropogenic activities represents one of the most prevalent environmental issues in karst spring catchments of northern China. In June 2021, a comprehensive study was conducted in the Jinan Spring Catchment (JSC), where 30 groundwater and surface water samples were collected. The sources and spatial distribution of nitrate pollution were systematically investigated through hydrochemical analysis combined with dual-isotope tracing techniques (δ<sup>15</sup>N<sub>NO3</sub> and δ<sup>18</sup>O<sub>NO3</sub>). Analytical results revealed that the predominant anion and cation sequences were HCO<sub>3</sub><sup>−</sup> > SO<sub>4</sub><sup>2−</sup> > Cl<sup>−</sup> > NO<sub>3</sub><sup>−</sup> and Ca<sup>2+</sup> > Na<sup>+</sup> > Mg<sup>2+</sup> > K<sup>+</sup>, respectively, with HCO<sub>3</sub>·SO<sub>4</sub>-Ca identified as the primary hydrochemical type. Notably, the average NO<sub>3</sub><sup>−</sup> concentration in groundwater (46.62 mg/L) significantly exceeded that in surface water (4.96 mg/L). Among the water samples, 11 locations exhibited substantial nitrate pollution, demonstrating an exceedance rate of 42%. Particularly, the NO<sub>3</sub><sup>−</sup>-N concentrations in both the upstream recharge area and downstream drainage area were markedly higher than those in the runoff area. The spatial distribution of NO<sub>3</sub><sup>−</sup> concentrations was primarily influenced by mixing processes, with no significant evidence of denitrification observed. The isotopic compositions ranged from −1.42‰ to 12.79‰ for δ<sup>15</sup>N<sub>NO3</sub> and 0.50‰ to 15.63‰ for δ<sup>18</sup>O<sub>NO3</sub>. Bayesian isotope mixing model (MixSIAR) analysis indicated that domestic sewage and manure constituted the principal nitrate sources, contributing 37.1% and 56.9% to groundwater and surface water, respectively. Secondary sources included soil organic nitrogen, rainfall and fertilizer NH<sub>4</sub><sup>+</sup>, and chemical fertilizers, while atmospheric deposition showed the lowest contribution rate. Additionally, potential mixing of soil organic nitrogen with chemical fertilizer was identified.https://www.mdpi.com/2305-6304/13/5/393karst groundwaterhydrochemical characteristicsstable isotopesnitratespatial distribution
spellingShingle Kairan Wang
Mingyuan Fan
Zhen Wu
Xin Zhang
Hongbo Wang
Xuequn Chen
Mingsen Wang
Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China
Toxics
karst groundwater
hydrochemical characteristics
stable isotopes
nitrate
spatial distribution
title Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China
title_full Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China
title_fullStr Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China
title_full_unstemmed Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China
title_short Using Geochemistry, Stable Isotopes and Statistical Tools to Estimate the Sources and Transformation of Nitrate in Groundwater in Jinan Spring Catchment, China
title_sort using geochemistry stable isotopes and statistical tools to estimate the sources and transformation of nitrate in groundwater in jinan spring catchment china
topic karst groundwater
hydrochemical characteristics
stable isotopes
nitrate
spatial distribution
url https://www.mdpi.com/2305-6304/13/5/393
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