Hexavalent chromium is a heavy metal used in a variety of industrial applications which is highly toxic to humans, animals, plants and microorganisms. Moreover, it is a well-established human carcinogen by the inhalation route of exposure and a possible human carcinogen by the oral route of exposure. Therefore, it should be removed from contaminated waters. Its reduction to trivalent chromium can be beneficial because a more mobile and more toxic chromium species is converted to a less mobile and less toxic form. During the last two decades, there has been important interest in using zero-valent iron (ZVI) as a Cr(VI)-reducing agent. A considerable volume of research has been carried out in order to investigate the mechanism and kinetics of Cr(VI) reduction with ZVI, as well as the influence of various parameters controlling the reduction efficiency. Therefore, the purpose of this review was to provide updated information regarding the developments and innovative approaches in the use of ZVI for the treatment of Cr(VI)-polluted waters.

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Hexavalent chromium (Cr VI ) compounds are used in a variety of industrial applications and, as a result, large quantities of Cr VI have been released into the environment due to inadequate precautionary measures or accidental releases. Cr VI is highly toxic to most living organisms and a known human carcinogen by inhalation route of exposure. Another major issue of concern about Cr VI compounds is their high mobility, which easily leads to contamination of surface waters, soil, and ground waters. In recent years, attention has been focused on the use of metallic iron (Fe 0 ) for the abatement of Cr VI polluted waters. Despite a great deal of research, the mechanisms behind the efficient aqueous Cr VI removal in the presence of Fe 0 (Fe 0 /H 2 O systems) remain deeply controversial. The introduction of the Fe 0 -based filtration technology, at the beginning of 1990s, was coupled with the broad consensus that direct reduction of Cr VI by Fe 0 was followed by co-precipitation of resulted cations (Cr III , Fe III ). This view is still the dominant removal mechanism (reductive-precipitation mechanism) within the Fe 0 remediation industry. An overview on the literature on the Cr geochemistry suggests that the reductive-precipitation theory should never have been adopted. Moreover, recent investigations recalling that a Fe 0 /H 2 O system is an ion-selective one in which electrostatic interactions are of primordial importance is generally overlooked. The present work critically reviews existing knowledge on the Fe 0 /Cr VI /H 2 O and Cr VI /H 2 O systems, and clearly demonstrates that direct reduction with Fe 0 followed by precipitation is not acceptable, under environmental relevant conditions, as the sole/main mechanism of Cr VI removal in the presence of Fe 0 .

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