Uncatalyzed and catalyzed nanoscale Fe(0) systems were employed for the denitrification of unbuffered 40 mgN L(-1) nitrate solutions at initial neutral pH. Compared to microscale Fe(0) (<100 mesh), the efficiency and rate of nitrate removal using uncatalyzed and catalyzed nano-Fe(0) were highly promoted, in which the maximum promoted rate was obtained using copper-catalyzed nano-Fe(0) (nano-Cu/Fe). Nitrate first-order degradation rate constants (k(obs)) decreased significantly (>70%) with aged nano-Fe(0) and aged nano-Cu/Fe, and were recovered with NaBH(4) as reductants at levels of about 85 and 75%, respectively. Activation energies (E(a)) of nitrate reduction over the temperature range of 10-60 degrees C were 42.5 kJ mol(-1) for microscale Fe(0), 25.8 kJ mol(-1) for nano-Fe(0) and 16.8 kJ mol(-1) for nano-Cu/Fe. Unlike microscale Fe(0), the kinetics of denitrification by nano-Fe(0) and nano-Cu/Fe began to show characteristics of mass transport in addition to chemical reaction control. Ammonium was the predominant end product in all the systems. However, as for nitrite, 40% of the degraded nitrate persisted in the nano-Cu/Fe system. Thus, relative to nano-Cu/Fe, nano-Fe(0) is a potential reductant for denitrification of groundwater as far as toxic nitrite generation is concern.
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