Selective ionic liquid solvent bar micro-extraction for estimation of ultra-trace silver fractions in marine waters

Ag can be found in the ocean at the ultra-trace level, mainly as AgCl_n^(n-1)- and complexed by dissolved organic matter (Ag-DOM). However, methods for studying Ag speciation in marine waters are limited by the lack of extractants capable to separate organic and inorganic silver species in natural conditions of seawater samples. In this work, a two-phase solvent bar micro-extraction method using the ionic liquid trihexyltetradecylphosphonium chloride (Cyphos® 101) was applied for selective micro-extraction of AgCl_n^(n-1)- from organic silver in marine waters, working at seawater pH,. The application to real samples was performed under the following conditions: 2.5% Cyphos® 101 in kerosene solution with 10% dodecan-1-ol inside the fiber, and 30 min of sample extraction at a stirring rate of 800 rpm. The proposed SBME was successfully used for estimation of Ag fractions in waters from the Bay of Cádiz (South-west Spain) showing its applicability for a simple, fast and environmentally friendly speciation of silver in marine water samples. The method presented a linear response up to 500 ng L^-1 and a detection limit of 0.4 ng L^-1, using GF-AAS for instrumental determination.