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Identifying the sources and transformations of riverine nitrate plays a critical role in mitigating nitrogen enrichment of river networks. Several previous studies have used δ18O-NO3− to quantitatively assess riverine nitrate contributed by atmospheric nitrate and terrestrial sources, but their results have great uncertainty due to the wide range of δ18O-NO3− values and isotopic fractionation during nitrogen-cycling processes in terrestrial environment. The nitrate 17O anomaly (△17O-NO3−), as an unambiguous tracer of atmospheric nitrate, is a promising tool to effectively separate atmospheric nitrate from microbially produced nitrate. However, to our knowledge, △17O-NO3− approach has not been previously applied to identify nitrate pollution sources in plain river networks of eastern China. In this study, we used a multiple isotope approach (δD/δ18O-H2O and δ15N/δ18O/△17O-NO3−) for the first time to quantitatively identify sources and transformations of riverine nitrate in a hypereutrophic coastal plain river network namely Wen-Rui Tang River located in eastern China, which is a region receiving high inputs of atmospheric nitrogen deposition. The △17O-NO3− values in precipitation and river water during the study period (April–June of 2021) varied from 14.83‰ to 31.39‰ and from − 2.82‰ to 9.66‰, respectively. The δD/δ18O-H2O values revealed that river water mainly originated from recent precipitation with little evaporation. Moreover, the δ15N/δ18O-NO3− values indicated that microbial nitrification, not denitrification, was the predominant nitrogen-cycling process in the watershed. Based on a Bayesian mixing model (Stable Isotope Analysis in R, SIAR) using δ15N/△17O-NO3−, municipal sewage was identified as the dominant nitrate source (50.5 ± 11.7%), followed by soil nitrogen (23.8 ± 13.7%), atmospheric nitrate deposition (14.3 ± 2.9%), and nitrogen fertilizer (11.4 ± 8.7%). Finally, an uncertainty analysis for nitrate source apportionment demonstrated that the greatest uncertainty was associated with soil nitrogen, followed by municipal sewage, nitrogen fertilizer, and atmospheric nitrate deposition. This study provides important scientific information on riverine nitrate source apportionment to guide pollution control/remediation strategies and highlights the benefits of utilizing △17O-NO3− to enhance nitrate source apportionment.

Heavy metal pollution of aquatic environments in rapidly developing industrial regions is of considerable global concern due to its potential to cause serious harm to aquatic ecosystems and human health. This study assessed heavy metal contamination of sediments in a highly industrialized urban watershed of eastern China containing several historically unregulated manufacturing enterprises. Total concentrations and solid-phase fractionation of Cu, Zn, Pb, Cr and Cd were investigated for 39 river sediments using multivariate statistical analysis and geographically weighted regression (GWR) methods to quantitatively examine the relationship between land use and heavy metal pollution at the watershed scale. Results showed distinct spatial patterns of heavy metal contamination within the watershed, such as higher concentrations of Zn, Pb and Cd in the southwest and higher Cu concentration in the east, indicating links to specific pollution sources within the watershed. Correlation and PCA analyses revealed that Zn, Pb and Cd were dominantly contributed by anthropogenic activities; Cu originated from both industrial and agricultural sources; and Cr has been altered by recent pollution control strategies. The GWR model indicated that several heavy metal fractions were strongly correlated with industrial land proportion and this correlation varied with the level of industrialization as demonstrated by variations in local GWR R2 values. This study provides important information for assessing heavy metal contaminated areas, identifying heavy metal pollutant sources, and developing regional-scale remediation strategies.

Accurate quantification of dissolved oxygen (DO) is critically important for managing water resources and controlling pollution. Artificial intelligence (AI) models have been successfully applied for modeling DO content in aquatic ecosystems with limited data. However, the efficacy of these AI models in predicting DO levels in the hypoxic river systems having multiple pollution sources and complicated pollutants behaviors is unclear. Given this dilemma, we developed a promising AI model, known as support vector machine (SVM), to predict the DO concentration in a hypoxic river in southeastern China. Four different calibration models, specifically, multiple linear regression, back propagation neural network, general regression neural network, and SVM, were established, and their prediction accuracy was systemically investigated and compared. A total of 11 hydro-chemical variables were used as model inputs. These variables were measured bimonthly at eight sampling sites along the rural-suburban-urban portion of Wen-Rui Tang River from 2004 to 2008. The performances of the established models were assessed through the mean square error (MSE), determination coefficient (R 2), and Nash-Sutcliffe (NS) model efficiency. The results indicated that the SVM model was superior to other models in predicting DO concentration in Wen-Rui Tang River. For SVM, the MSE, R 2, and NS values for the testing subset were 0.9416 mg/L, 0.8646, and 0.8763, respectively. Sensitivity analysis showed that ammonium-nitrogen was the most significant input variable of the proposal SVM model. Overall, these results demonstrated that the proposed SVM model can efficiently predict water quality, especially for highly impaired and hypoxic river systems.

As an important regulator of pollutants in overland flow and interflow, land use has become an essential research component for determining the relationships between surface water quality and pollution sources. This study investigated the use of ordinary least squares (OLS) and geographically weighted regression (GWR) models to identify the impact of land use and population density on surface water quality in the Wen-Rui Tang River watershed of eastern China. A manual variable excluding-selecting method was explored to resolve multicollinearity issues. Standard regression coefficient analysis coupled with cluster analysis was introduced to determine which variable had the greatest influence on water quality. Results showed that: (1) Impact of land use on water quality varied with spatial and seasonal scales. Both positive and negative effects for certain land-use indicators were found in different subcatchments. (2) Urban land was the dominant factor influencing N, P and chemical oxygen demand (COD) in highly urbanized regions, but the relationship was weak as the pollutants were mainly from point sources. Agricultural land was the primary factor influencing N and P in suburban and rural areas; the relationship was strong as the pollutants were mainly from agricultural surface runoff. Subcatchments located in suburban areas were identified with urban land as the primary influencing factor during the wet season while agricultural land was identified as a more prevalent influencing factor during the dry season. (3) Adjusted R2 values in OLS models using the manual variable excluding-selecting method averaged 14.3% higher than using stepwise multiple linear regressions. However, the corresponding GWR models had adjusted R2 ~59.2% higher than the optimal OLS models, confirming that GWR models demonstrated better prediction accuracy. Based on our findings, water resource protection policies should consider site-specific land-use conditions within each watershed to optimize mitigation strategies for contrasting land-use characteristics and seasonal variations.

In the context of water resource management and pollution control, the characterization of water quality impairments and identification of dominant pollutants are of critical importance. In this study, water quality impairment was assessed on the basis of 7 hydrochemical variables that were monitored bimonthly at 17 sites in 2010 along the rural-suburban-urban portion of the Wen-Rui Tang River in eastern China. Seven methods were used to assess water quality in the river system. These methods included single-factor assessment, water quality grading, comprehensive pollution index, the Nemerow pollution index, principle component analysis, fuzzy comprehensive evaluation, and comprehensive water quality identification index. Our analysis showed that the comprehensive water quality identification index was the best method for assessing water quality in the Wen-Rui Tang River due to its ability to effectively characterize highly polluted waters with multiple impairments. Furthermore, a guideline for the applications of these methods was presented based on their characteristics and efficacy. Results indicated that the dominant pollutant impairing water quality was total nitrogen comprised mainly of ammonium. The temporal variation of water quality was closely related to precipitation as a result of dilution. The spatial variation of water quality was associated with anthropogenic influences (urban, industrial, and agriculture activities) and water flow direction (downstream segments experiencing cumulative effects of upstream inputs). These findings provide valuable information and guidance for water pollution control and water resource management in highly polluted surface waters with multiple water quality impairments in areas with rapid industrial growth and urbanization.

In the context of water resource management and pollution control, the characterization of water quality impairments and identification of dominant pollutants are of critical importance. In this study, water quality impairment was assessed on the basis of 7 hydrochemical variables that were monitored bimonthly at 17 sites in 2010 along the rural-suburban-urban portion of theWen-Rui Tang River in eastern China. Seven methods were used to assess water quality in the river system. These methods included single-factor assessment, water quality grading, comprehensive pollution index, the Nemerow pollution index, principle component analysis, fuzzy comprehensive evaluation, and comprehensive water quality identification index. Our analysis showed that the comprehensive water quality identification index was the best method for assessing water quality in the Wen-Rui Tang River due to its ability to effectively characterize highly polluted waters with multiple impairments. Furthermore, a guideline for the applications of these methods was presented based on their characteristics and efficacy. Results indicated that the dominant pollutant impairing water quality was total nitrogen comprised mainly of ammonium. The temporal variation of water quality was closely related to precipitation as a result of dilution. The spatial variation of water quality was associated with anthropogenic influences (urban, industrial, and agriculture activities) and water flow direction (downstream segments experiencing cumulative effects of upstream inputs). These findings provide valuable information and guidance for water pollution control and water resource management in highly polluted surface waters with multiple water quality impairments in areas with rapid industrial growth and urbanization. [ABSTRACT FROM AUTHOR]

[Display omitted] • △17O-NO 3 − was firstly used to trace riverine nitrate sources in eastern China. • Nitrification was identified as dominant nitrogen-cycling process by δ 15N/ δ 18O-NO 3 −. • δ 15N/△17O-NO 3 − and SIAR modeling determined MS as the primary nitrate source. • Uncertainties of source contributions decreased in the order: SN > MS > NF > AD. Identifying the sources and transformations of riverine nitrate plays a critical role in mitigating nitrogen enrichment of river networks. Several previous studies have used δ 18O-NO 3 − to quantitatively assess riverine nitrate contributed by atmospheric nitrate and terrestrial sources, but their results have great uncertainty due to the wide range of δ 18O-NO 3 − values and isotopic fractionation during nitrogen-cycling processes in terrestrial environment. The nitrate 17O anomaly (△17O-NO 3 −), as an unambiguous tracer of atmospheric nitrate, is a promising tool to effectively separate atmospheric nitrate from microbially produced nitrate. However, to our knowledge, △17O-NO 3 − approach has not been previously applied to identify nitrate pollution sources in plain river networks of eastern China. In this study, we used a multiple isotope approach (δ D/ δ 18O-H 2 O and δ 15N/ δ 18O/△17O-NO 3 −) for the first time to quantitatively identify sources and transformations of riverine nitrate in a hypereutrophic coastal plain river network namely Wen-Rui Tang River located in eastern China, which is a region receiving high inputs of atmospheric nitrogen deposition. The △17O-NO 3 − values in precipitation and river water during the study period (April–June of 2021) varied from 14.83‰ to 31.39‰ and from − 2.82‰ to 9.66‰, respectively. The δ D/ δ 18O-H 2 O values revealed that river water mainly originated from recent precipitation with little evaporation. Moreover, the δ 15N/ δ 18O-NO 3 − values indicated that microbial nitrification, not denitrification, was the predominant nitrogen-cycling process in the watershed. Based on a Bayesian mixing model (Stable Isotope Analysis in R, SIAR) using δ 15N/△17O-NO 3 −, municipal sewage was identified as the dominant nitrate source (50.5 ± 11.7%), followed by soil nitrogen (23.8 ± 13.7%), atmospheric nitrate deposition (14.3 ± 2.9%), and nitrogen fertilizer (11.4 ± 8.7%). Finally, an uncertainty analysis for nitrate source apportionment demonstrated that the greatest uncertainty was associated with soil nitrogen, followed by municipal sewage, nitrogen fertilizer, and atmospheric nitrate deposition. This study provides important scientific information on riverine nitrate source apportionment to guide pollution control/remediation strategies and highlights the benefits of utilizing △17O-NO 3 − to enhance nitrate source apportionment. [ABSTRACT FROM AUTHOR]

Water quality has degraded dramatically in Wen-Rui Tang River watershed, Zhejiang, China, especially due to rapid economic development since 1995. This paper aims to assess spatial and temporal variations of the main pollutants (NH $_{4}^{+}$-N, TN, BOD, COD, DO) of water quality in Wen-Rui Tang River watershed, using the geographic information system, cluster analysis (CA) and principal component analysis (PCA). Results showed that concentrations of BOD, COD, NH $_{4}^{+}$-N, and TN were significantly higher in tertiary rivers than in primary and secondary rivers. From April 2006 to March 2007, the concentrations of NH $_{4}^{+}$-N (2.25-57.9 mg/L) and TN (3.78-70.4 mg/L) in all samples exceeded Type V national water quality standards (≥2 mg/L), while 5.3% of all COD (1.83-27.5 mg/L) and 33.6% of all BOD (0.34-50.4 mg/L) samples exceeded Type V national water quality standards (COD ≥ 15 mg/L, BOD ≥ 10 mg/L). Monthly changes of pollutant concentrations did not show a clear pattern, but correlation analysis indicated that NH $_{4}^{+}$-N and TN in tertiary rivers had a significant negative correlation with 5-day cumulative rainfall and monthly rainfall, while there were no significant correlations in primary and secondary rivers. The results of CA and spatial analysis showed that the northern part of Wen-Rui Tang River watershed was the most seriously polluted. This region is characterized by the high population density and industrial and commercial activities. The PCA and spatial analysis indicated that the degraded water quality is caused by anthropogenic activities and poor wastewater management. [ABSTRACT FROM AUTHOR]

Heavy metal pollution of aquatic environments in rapidly developing industrial regions is of considerable global concern due to its potential to cause serious harm to aquatic ecosystems and human health. This study assessed heavy metal contamination of sediments in a highly industrialized urban watershed of eastern China containing several historically unregulated manufacturing enterprises. Total concentrations and solid-phase fractionation of Cu, Zn, Pb, Cr and Cd were investigated for 39 river sediments using multivariate statistical analysis and geographically weighted regression (GWR) methods to quantitatively examine the relationship between land use and heavy metal pollution at the watershed scale. Results showed distinct spatial patterns of heavy metal contamination within the watershed, such as higher concentrations of Zn, Pb and Cd in the southwest and higher Cu concentration in the east, indicating links to specific pollution sources within the watershed. Correlation and PCA analyses revealed that Zn, Pb and Cd were dominantly contributed by anthropogenic activities; Cu originated from both industrial and agricultural sources; and Cr has been altered by recent pollution control strategies. The GWR model indicated that several heavy metal fractions were strongly correlated with industrial land proportion and this correlation varied with the level of industrialization as demonstrated by variations in local GWR R 2 values. This study provides important information for assessing heavy metal contaminated areas, identifying heavy metal pollutant sources, and developing regional-scale remediation strategies., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

As an important regulator of pollutants in overland flow and interflow, land use has become an essential research component for determining the relationships between surface water quality and pollution sources. This study investigated the use of ordinary least squares (OLS) and geographically weighted regression (GWR) models to identify the impact of land use and population density on surface water quality in the Wen-Rui Tang River watershed of eastern China. A manual variable excluding-selecting method was explored to resolve multicollinearity issues. Standard regression coefficient analysis coupled with cluster analysis was introduced to determine which variable had the greatest influence on water quality. Results showed that: (1) Impact of land use on water quality varied with spatial and seasonal scales. Both positive and negative effects for certain land-use indicators were found in different subcatchments. (2) Urban land was the dominant factor influencing N, P and chemical oxygen demand (COD) in highly urbanized regions, but the relationship was weak as the pollutants were mainly from point sources. Agricultural land was the primary factor influencing N and P in suburban and rural areas; the relationship was strong as the pollutants were mainly from agricultural surface runoff. Subcatchments located in suburban areas were identified with urban land as the primary influencing factor during the wet season while agricultural land was identified as a more prevalent influencing factor during the dry season. (3) Adjusted R 2 values in OLS models using the manual variable excluding-selecting method averaged 14.3% higher than using stepwise multiple linear regressions. However, the corresponding GWR models had adjusted R 2 ~59.2% higher than the optimal OLS models, confirming that GWR models demonstrated better prediction accuracy. Based on our findings, water resource protection policies should consider site-specific land-use conditions within each watershed to optimize mitigation strategies for contrasting land-use characteristics and seasonal variations., (Copyright © 2016 Elsevier B.V. All rights reserved.)