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Rainwater chemistry plays an important role in the earth-surficial ecosystem, but studies on rainwater chemical composition of karst agro-ecosystem are rare. To explore the rainwater alkalization and the provenance of components responsible for neutralization, two-years chemical monitoring of rainwater was carried out in a karst agricultural catchment in Southwest China. The main findings suggest that SO 4 2- , NO 3 - , Ca 2+ , and NH 4 + are the principal ions. All the ionic contents show distinctly seasonal variation (highest in winter) in response to variations in seasonal precipitation because the rain-scour process can efficiently remove atmospheric materials. Source identification indicates that Cl - and Na + are mainly derived from marine input whereas SO 4 2- and NO 3 - are controlled by anthropogenic emission, in particular, fixed emission sources. The source of NH 4 + is attributed to intense agricultural production, while Ca 2+ and Mg 2+ are mainly derived from calcite dissolution. The rainwater alkalization caused by the seasonal acid neutralization (via basic components, Ca 2+ and NH 4 + ) is beneficial to crop growth but also reflect agricultural overfertilization. Sulfur controlled the total wet acid deposition (68%-94%) and could be a potential agent of weathering., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Understanding where nitrate is mobilized from and under what conditions is required to reduce nitrate loss and protect water quality. Low frequency sampling may inadequately capture hydrological and biogeochemical processes that will influence nitrate behavior. We used high-frequency isotope sampling and in-situ nitrate sensing to explore nitrate export and transformation in a karst critical zone. Nitrate was mobilised during light rainfall, and transferred from soil layers to the karst matrix, where some nitrate was retained and denitrified. Nitrate isotopic composition changed rapidly during the rising limb of events and slowly during the falling limb. The main nitrate source was synthetic fertiliser (up to 80% during event flow), transported by conduit flow following high rainfall events, and this contribution increased significantly as discharge increased. Soil organic nitrogen contribution remained constant indicating at baseflow this is the primary source. Isotope source appointment of nitrate export revealed that synthetic fertilizer accounted for more than half of the total nitrate export, which is double that of the secondary source (soil organic nitrogen), providing valuable information to inform catchment management to reduce nitrate losses and fluvial loading. Careful land management and fertilizer use are necessary to avoid nitrate pollution in the karst agroecosystem, for example by timing fertilizer applications to allow for plant uptake of nitrate before rainfall can flush it from the soils into the karst and ultimately into catchment drainage., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

Emission of reactive nitrogen species has a major impact on atmospheric chemistry, ecosystem and human health. The origin and formation mechanisms of wet-deposited nitrate are not well understood in Southeast Asia (SEA). In this study, we measured stable isotopes of nitrate (δ 15 N and δ 18 O) and chemical compositions of daily rainwater from May 2015 to July 2017 in Singapore. Our results showed that δ 15 N-NO 3 - and δ 18 O-NO 3 - varied seasonally with higher values during the Inter-monsoon period (April-May and October-November) than during Northeast (December-March) and Southwest monsoon (June-September). Bayesian mixing modeling, which took account of the isotope fractionation, indicated that traffic emission (47 ± 32%) and lightning (19 ± 20%) contributed the most to NO 3 - with increased traffic contribution (55 ± 37%) in the Northeast monsoon and lightning (24 ± 23%) during the Inter-monsoon period. Biomass burning and coal combustion, likely from transboundary transport, contributed ∼25% of nitrate in the rainwater. Monte Carlo simulation of δ 18 O-NO 3 - indicated that oxidation process by hydroxyl radical contributed 65 ± 14% of NO 3 - , with the rest from hydrolysis of N 2 O 5 . Wind speed had large effect on δ 18 O-NO 3 - variations in the atmosphere with more involvement of hydroxyl radical reactions when wind speed increased. Our study highlights the key role of isotopic fractionation in nitrate source apportionment, and the influence of meteorological conditions on nitrate formation processes in SEA., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Nitrogenous species, particularly nitrate, are some of the most significant contaminants in freshwater rivers and lakes in China, posing a significant threat to human and ecosystem health. To identify the major nitrate sources and transformation processes in a subtropical karst lake (Hongfeng, HF) in Southwest China, two sampling campaigns involving three lake profiles were conducted during the impoundment period (April) and flood period (August). Hydro-chemistry parameters, concentration of nitrogenous species, and dual isotopes of nitrate were analyzed. Nitrate was the major nitrogenous species in HF lake with higher proportion in April than August. The concentrations of NH4+, NO2- and dissolved organic nitrogen were below the detection limit in April, while NH4+ increased with depth in August, which may be a result of mineralization. Nitrification was detected during the impoundment period and from the surface to a depth of 10 m during the flood period. Denitrification was detected in the lake bottom waters during the flood period with isotopic fractionation of -10.7‰ for δ15N-NO3- and -4.7‰ for δ18O-NO3-. The Rayleigh distillation demonstrated denitrification showed spatial variation (53% and 89% of nitrate in the southern and northern region of the lake, respectively). The Bayesian modelling results suggest that organic nitrogen degradation and sediment make the largest contributions to nitrate (51% and 38% in April and 33% and 24% in August, respectively) to the lake. Tributaries contributed more nitrate in August (37%) than in April (10%). The results highlight that modified endogenous nitrogen contributed a high proportion of nitrate sources within the lake system during the two periods.