Reactivity and fluxes of antimony in a macrotidal estuarine salinity gradient: Insights from single and triple quadrupole ICP-MS performances

Trace element analyses in brackish waters are challenging for many elements at ppb/ppt levels and analytical methods. In this work, we compare two methods using inductively coupled plasma mass spectrometry (ICP-MS) for quantifying antimony (Sb). Results of a previous study along the salinity gradient in a macrotidal estuary (i.e., the Gironde Estuary, France) using isotopic dilution via single quadrupole ICP-MS are compared to reanalyzed aliquots of the same samples. Direct analyses of estuarine water samples via standard additions (N = 52) were performed with a QQQ-ICP-MS (new generation, iCAP TQ Thermo®) to determine dissolved (< 0.2 μm filtered and UV-irradiated replicates) Sb concentrations during two contrasting hydrological conditions (low vs high freshwater discharges). Despite following good analytical practices on both studies, the use of the new analytical device provides more robust results and highlighted a characteristic ¹²¹Sb isotopic interference in estuarine samples at S > 20, efficiently eliminated by the QQQ-ICP-MS performance. This means that Sb reactivity shows an additive, non-conservative behavior in the Gironde Estuary, with a more defined bell-shaped profile in low discharge compared to high discharge conditions. This approach allows to quantify for the first time in the literature Sb dissolved net fluxes from the Gironde Estuary to the Atlantic coast and provides an updated value for the seawater endmember. This study opens future applications of QQQ-ICP-MS for quantifying on a more routine basis dissolved trace elements in brackish waters, providing guidelines and good practices for field studies regarding Sb determination in estuarine systems.