The mechanisms controlling arsenic mobility, including competition with
oxyanion ortho-phosphate, in the subsurface and in laboratory controlled experiments
were investigated. Additionally, the solubility and meta-stability of GR as a sorbing
surface for arsenic in sub-oxic environments was examined. A systems approach was
employed to: 1) investigate a model system constrained by thermodynamic constants
and a well defined field site, 2) examine a synthetic system to elucidated the effects of
co-precipitating oxyanions of arsenic and phosphate with GR, a scenario expected as
an environment transitions from oxic to suboxic conditions, and 3) to study the abiotic
conditions where GR formation is favorable in suboxic conditions. A systems
approach, defined here as the method of investigating a problem by looking at
individual but inter-dependent components in the broader context of a larger
interdisciplinary environment, was employed to investigate GR in natural and
laboratory controlled settings.
This research has investigated the mineralogical response, and subsequent
surface complexation reactions, to a redox change from oxic to sub oxic conditions.
A redox gradient is commonly encountered in nature, observed in wetlands and from
flooding sediments. These findings can be applied to a contaminant management
plan, and may be important when considering the anticipated precipitation pattern
changes due to global climate change. The overall goal of this study was to
characterize mineralogical structural changes and solubilities of the solid phase iron
sorbate host and the dissolved constituents (incl. nutrients and contaminants) in
suboxic environments. Generally, suboxic environments are found in wetlands and
submerged soils. Because wetlands accumulate dissolved ions from a vast watershed,
a geochemical response to a hydrologic perturbation will likely affect contaminant and
nutrient cycling in the region, and should be included in any management response.
Iron is one of the most abundant elements in soils and the most abundant redox active
element in natural systems, is generally dissolved as a reduced species (FeII) and
insoluble as an oxidized species (FeIII). Therefore, iron transitions are principally
controlled by the availability of oxygen. The result is a variety of iron oxide and
hydroxide mineral phases that are stable and meta-stable under different soil PO2
conditions. Due to the transient variability between the aqueous Fe(II) and solid phase
Fe(III) redox states, iron plays a major role in controlling the nutrient and contaminant
cycling in subsurface environment. This research has investigated green rusts that
may form at the redox boundary between fully oxidized and sub oxic sediments (Root
et al. 2007, 2009). A primary goal of this research was to increase the scientific
knowledge base concerning arsenic clean up and remediation, removal from the
drinking water supply, and sequestration in the solid phase thereby isolating arsenic
from uptake into the biota.