Identifying the source and transformation of riverine nitrates in a karst watershed, North China: Comprehensive use of major ions, multiple isotopes and a Bayesian model

Abstract

Nitrate (NO3−) contamination of surface water is a globally concern, especially in karstic regions affected by intensive agricultural activities. This study combines hydrochemistry, and environmental isotopes (δ2HH2O, δ18OH2O, δ15NNO3, and δ18ONO3) with a Bayesian isotope mixing model (Simmr) to reduce the uncertainty in estimating the contributions of different pollution sources. Samples were collected from 32 surface water sites in the Yufu River (YFR) watershed, North China, in September and December 2019. The results revealed that NO3−-N was the predominant form of inorganic nitrogen that caused the deterioration of water quality in the watershed, accounting for approximately 58% of the total nitrogen (TN). The hydrochemical compositions and nitrate isotopes indicated that NO3− mainly originated from soil nitrogen (SN), ammonium fertilizer (AF), but nitrate fertilizer (NF), manure and sewage (M&S) and atmospheric precipitation (AP) were limited. The isotopic composition of nitrate in the upper reaches of the watershed was mainly affected by microbial nitrification, while the mixture of multiple sources was the dominant nitrogen transformation process in the mid-lower reaches of the watershed. Simmr model outputs revealed that SN (56.5%) and AF (29.5%) were the primary contributor to riverine NO3− pollution, followed by NF (7.1%), MS (3.6%), and AP (3.4%) sources. Moreover, an uncertainty index (UI90) of the isotope mixing showed that SN (0.73) and AF (0.67) had the highest values, followed by NF (0.22), M&S (0.22) and AP (0.10). Chemical fertilizer and SN collectively contributed >50% of nitrate during the two sampling campaigns. These results indicated that reducing the application of nitrogen fertilizers and rational irrigation are the keys to alleviate of NO3− pollution. The study is helpful in understanding the source and transformation of riverine NO3− and effectively reducing NO3− pollution in karst agricultural rivers or watersheds.