ABSTRACT
Fluvial organic carbon (OC) transfer is an essential resource for downstream ecosystems. Multiple factors affect its transfer process, e.g., climate or anthropogenic activities. Quantifying OC fluxes with fine spatiotemporal resolution is challenging in anthropised catchments. This study aims to quantify daily OC dynamics and to assess the impacts of short climate variability and damming on OC spatiotemporal transfer processes in a large tropical Asian river basin (the Red River) for an extended period (2003-2013) by combining empirical equations with modelling outputs. Firstly, empirical equations for calculating dissolved (DOC) and particulate OC (POC) concentrations were calibrated based on in-situ sampling data. Then, simulated daily discharge (Q) and suspended sediment concentrations were used to quantify daily OC fluxes. Results show that the parameters of the DOC and POC equations well represent the subbasins characteristics, underlining the effects of soil OC content, mean annual Q and Chlorophyll a. DOC and POC exports reached 222 and 406 kt yr-1 at the basin outlet, accounting for 0.38 % of the total OC (TOC) exported by Asian rivers to the ocean. However, the specific yields of DOC (1.62 t km-2 yr-1) and POC (2.96 t km-2 yr-1) of the Red River basin were ~ 1.5 times those of other Asian basins. By comparing a reference scenario (without dams) to current conditions, we estimated 12 % and 88 % decreases in DOC and POC fluxes between 2008-2013 and 2003-2007, mainly due to damming. This study shows that climate variability may not impact OC dynamics in rivers as it explained <2 % of the variations. However, dam management, especially recent ones operating since 2008, deeply influences OC variations as the POC/TOC ratio decreased from 86 % to 47 %. Damming significantly decreased POC exports due to sediment retention, altering the equilibrium of OC cycling downstream, which may impact the food chain.
ABSTRACT
A new green method for trace level quantification of four herbicides, glyphosate (GLYP), glufosinate (GLUF), and their main metabolites, aminomethylphosphonic acid (AMPA) and 3-(methyl-phosphinico)-propionic acid (MPPA), was developed. The purification step without any derivatization was conducted by solid-phase extraction using Chelex-100 resin in the Fe (III) form, followed by elution with 5% NH4OH. The four analytes were quantified by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. The developed extraction method was validated on five fresh and sea water matrices with mean recoveries ranging from 80.1% to 109.4% (relative standard deviation < 20%). The extraction conditions were evaluated and certified for the high applicability of the extraction method too. The limits of detection (ng/L) in the five water matrices were in ranges 0.70 - 4.0, 2.4 - 3.9, 1.8 - 4.7, and 1.6 - 4.0 for GLYP, AMPA, GLUF, and MPPA, respectively. The method was successfully applied to detect the four compounds in surface waters sampled along the Red River Delta region in July 2019. The highest concentrations were detected at 565, 1,330, 234, and 871 ng/L for GLYP, AMPA, GLUF, and MPPA, respectively. These results showed the potential capacity of this new method for convenient monitoring of herbicides and their metabolites in the diverse natural water system.
