Natural organic matter as reductant for chlorinated aliphatic pollutants

Humic acids (HA) are ubiquitous redox-active compounds of natural aquatic and soil systems. Here we studied the potential of HA as reductants for chlorinated aliphatic pollutants. To avoid artifacts potentially involved when studying chemically reduced HA, we prepared electrochemically reduced soil, aquatic and synthetic HA, and anthrahydroquinone-2,6-disulfonic acid (AHQDS), a model compound for hydroquinone moieties in HA. Both reduced HA and AHQDS reduced hexachloroethane (HCE) at appreciable rates. Some reduction of HCE by HA, however, occurred even before electrochemical reduction of the humic acids. This indicates that a small fraction of reduced moieties in HA persists at oxic conditions for some time. The initial reaction followed pseudo-first-order reaction kinetics, and tetra chloroethylene was the only halogenated product. The relatively small variations in carbon-normalized rate constants, k(DOC), found indicate that despite inherent variations in concentration, accessibility, and reactivity of redox-active groups in HA of various origins their overall dechlorination activity is fairly constant. However, HCE transformation rate constants and reducing capacities of different HA did not correlate. Rate constants normalized to both carbon content and reducing capacity of HA clearly indicate that reduced functional groups in different HA exhibit different reactivities. Our results together with the fact that reduced HA can be formed by a variety of microbiological and chemical processes suggest that HA could play a significant role as reductants in the reductive transformation of subsurface contaminants and that such a process could potentially be enhanced at contaminated sites by addition of reducible natural organic matter.