Reduction of Tl(III) and oxidation of As(III), which are unstable speciation forms, start just after sampling as a result of disturbed chemical equilibrium. Separation of inorganic Tl and As species, unchanged, is thus crucial for reliable results of speciation analysis in water systems. Presented here a simple and fast sample pretreatment, based on ion exchange cartridges, which gives the possibility to separate Tl and As species already on the sampling site. Note the reduction of Tl(III) (15%) is in the range of losses typical for standard procedures based on Tl(III) fixation. The use of SCX-3 allows for Tl(III) and SAX for As(III) separation, which are then quantitated in the effluent by ICP-MS. Determination of non-retained species was done after reduction of the sample volume to 2 mL (50-fold preconcentration), which allowed for detection of As concentrations <0.1 ppb and Tl <0.01 ppb. For As, a collision chamber is required. The possibility of direct determination is very important for the forms being in trace amounts in sea water in the vicinity of harbors.