In this work, the third generation of flow injection analysis, that is, the so-called micro-Lab-on-Valve (μLOV) approach, is proposed for the first time for the separation, preconcentration and monitoring of metalloids as hyphenated with atomic fluorescence spectrometry (AFS). This was made feasible by interfacing the micromachined LOV-module with AFS by a multisyringe flowing stream network for on-line post column derivatization of the eluate aimed at the generation of hydride species. The potential of this new hyphenated technique for environmental assays was ascertained via the determination of ultratrace level concentrations of total inorganic arsenic in freshwater. Employing quantitative preoxidation of As(III) to As(V) in the samples by means of permanganate, the method involves the preconcentration of arsenate at pH 10 on a renewable anion exchanger, namely Q-Sepharose, packed in a LOV microcolumn. The analyte species is afterwards stripped out and concurrently pre-reduced by a 300 μL eluent plug containing 6 mol L-1 HCl and 10% KI. The eluate is downstream merged with a metered volume of sodium tetrahydroborate (0.3% w/v) for generation of arsine, which is subsequently quantified by AFS. The flow system facilitates on-column reduction of the retained arsenic with no need for application of programmable stopped-flow. Yet, the high concentration of reductant and extreme pH conditions for elution hinder the sorbent to be re-used due to the gradual deactivation of the functional moieties, so that maximum benefit can be taken from the application of the bead renewal strategy. The proposed procedure is characterized by a high tolerance to metal species and interfering hydride forming elements. In fact, ratios of Se(IV) to As ≤ 5000 and Sb(V) to As ≤ 500 are tolerated at the 10% interference level. Under the optimized experimental conditions, a detection limit (3σ) of 0.02 ng mL-1 As, a dynamic linear range of 0.05-2.0 ng mL-1 As (by tailoring the AFS gain), an enrichment factor of 8.8 for arsenate, and a precision better than 6.0% at the 0.1 ng mL-1 level were obtained for the bead-injection mode whenever the loading sample volume was affixed at 3.0 mL. The reliability and accuracy of the automated procedure was ascertained by determining total inorganic arsenic in both spiked environmental waters and certified reference materials of variable matrix complexity (TMDA-54.3 and ERM-CA010) at the low ng mL-1 level. No significant differences were found between the experimental results and the certified values at a significance level of 0.05.