<p>Activated carbon (AC) prepared from residual fly (FA) was activated by combined CO₂-steam&nbsp; gasification and physically modified with procaine hydrochloride (PQ⁺Cl^-). Modified AC was &nbsp;used as low cost and effective solid phase extractor (SPE) for removal, total determination &nbsp;and chemical speciation of chromium(III&amp;VI)&nbsp; in wastewater. &nbsp;&nbsp;Pseudo-second order rate equation is proposed for&nbsp; assigning the kinetics of chromium(VI) sorption in aqueous HCl (1.0 mol L^-1) by PQ⁺Cl^-- modified AC . The data were correlated with surface structure of the SPE. A dual&nbsp; separation mechanism of chromium(VI) &nbsp;as a binary complex ion associate [PQ⁺.CrO₃Cl^-] in/on the modified AC via &quot;weak base anion exchanger&quot; and an added component of &ldquo;surface adsorption&rdquo; is proposed.&nbsp; At 2 mL min^-1 flow rate Sorption of spiked chromium(VI) at known concentrations (0.5-20 mg mL^-1) from water onto modified AC packed columns at 2 mL min^-1 was achieved.&nbsp; The sorbed chromium(VI) species were successfully recovered (106.0&plusmn;2- 110 &plusmn;3%, n=3) from AC packed column with NaOH (10 mL, 1.0 mol L^-1). Chromium(III) after oxidation to chromium(VI) was also enriched&nbsp; and &nbsp;eluted from the AC packed column and analyzed. &nbsp;Modified PQ⁺Cl^- AC packed column was also used for &nbsp;total determination and speciation of &nbsp;chromium(III &amp; VI) species at trace levels &nbsp;in &nbsp;environmental water samples. Good apparent recovery percentage (94.6&plusmn;6.3-102.0&plusmn; 8.5 %) of chromium species was achieved confirming the analytical utility of the modified AC-packed column for removal, total determination and speciation of chromium(III &amp; VI) species in environmental water samples.</p>