A simple and sensitive method for the separation of Cr(III) in natural water was developed. The novel method was targeted on extraction of Cr(III) by using a nanometre-scale zirconium phosphate coated capillary tube, and determined by electrothermal atomic absorption spectrometry (ETAAS). The variables influencing the micro-extraction of Cr(III) including pH, sample volume, sample flow rate, eluent volume and eluent flow rate were investigated. Under the optimized conditions, the detection limit (3s) was 0.042 ng mL−1, and the relative standard deviation (RSD) was 1.5% (c = 10 ng mL−1, n = 7). The proposed method was applied to determination of Cr(III) in natural waters.
    
         
            
                     
                    
                        
                            
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