Devon Renock

Determining hematite content from NUV/Vis/NIR spectra: Limits of detection

Abstract Hematite occurs in various geologic settings including igneous, metamorphic, and sedimentary rocks as well as in soils. However, it frequently occurs at low concentrations, especially in soils, where it may be <1% by weight. Because hematite has the potential to be an indicator of oxidizing and climatic conditions in soils and paleosols, it is important to understand its limit of detection. In this paper we examine the limits of detection of hematite visually and with diffuse reflectance spectrophotometry (DRS) and X‑ray diffraction (XRD). To accomplish this we used a sample set consisting of “knowns” or calibration samples. These known samples consisted of 15 different matrices of varying mineral composition into which hematite in 7 different concentrations ranging from 0.01 to 4% by weight were mixed. Including the 0% hematite, our calibration data set consisted of 120 samples. Visually, hematite can be detected at a concentration of 0.01% by weight in a light matrix and 0.5% in the darkest of our matrices. However, because of metamerism, visual techniques cannot specifically identify hematite. We find that for both DRS and XRD the limit of detection is also dependent on the matrix. For XRD the limit of detection for hematite in bulk samples is about 1%. For DRS the limit of detection depends on the data reduction technique used. The commonly used Kubelka-Munk remission function and its first and second derivatives can easily identify hematite at the 0.5% level. However, the first derivative of the percent reflectance curve can detect hematite at 0.01% by weight in a light matrix and 0.05% in a dark matrix. We suggest that the first derivative of DRS curves is the best currently available method for qualitatively detecting the mineral hematite at low concentrations found in soils, sediments, and rocks. Work described in this paper may be applied in several situations. Our study of visual limits of hematite detection should aid field geologists in assessing hematite content. Analysis of color wavelength bands may also have application in remote sensing by indicating which bands are most sensitive to hematite, reported to be an important constituent of the martian surface. Furthermore, this study could help clarify remotely sensed terrestrial albedo changes, especially the Sahara/Sahel transition where the sediments change from light, quartz-dominated to dark, hematite-dominated. Our study also points out that with laboratory-based spectra the first derivative of the reflectance curve is the most sensitive transform for processing spectral data for hematite, thereby allowing concentrations as low as 0.01% to be detected.

Electrochemical Investigation of Arsenic Redox Processes on Pyrite

The specific Eh-pH conditions and mechanism(s) for the reduction of arsenite, As(III), by pyrite are incompletely understood. A fundamental question is what role the pyrite surface plays in the reduction process. We used electrochemical methods to evaluate the reduction of As(III) under controlled redox conditions. As(III) reduction to elemental As(0) occurs on the pyrite surface under suboxic-reducing conditions and is promoted at low pH. Remarkably, As(III) reduction on pyrite occurs at similar potentials to those for reduction on platinum metal, suggesting a similar mechanism and kinetics for these surfaces. The onset for As(III) reduction at pH ≤ 3.5 coincides with the potential for hydrogen electroadsorption on pyrite, E ≈ +0.1 V (versus RHE). Batch reactions show that As(III) is reduced on pyrite at the Eh-pH predicted by the electrochemical study. X-ray photoelectron spectroscopy reveals that, at pH ≤ 3.5, a significant fraction of the surface arsenic (30-60%) has an oxidation state consistent with As(0). Here, we propose a mechanism whereby atomic hydrogen that forms on ferric (hydr)oxide surface layers promotes As(III) reduction at low Eh and pH. Insights provided by this study will have implications for understanding the controls on dissolved As(III) concentrations in suboxic-anoxic environments.

Nutrient and pollutant metals within earthworm residues are immobilized in soil during decomposition

Earthworms are known to bioaccumulate metals, making them a potential vector for metal transport in soils. However, the fate of metals within soil upon death of earthworms has not been characterized. We compared the fate of nutrient (Ca, Mg, Mn) and potentially toxic (Cu, Zn, Pb) metals during decomposition of Amynthas agrestis and Lumbricus rubellus in soil columns. Cumulative leachate pools, exchangeable pools (0.1 M KCl + 0.01 M acetic acid extracted), and stable pools (16 M HNO3 + 12 M HCl extracted) were quantified in the soil columns after 7, 21, and 60 days of decomposition. Soil columns containing A. agrestis and L. rubellus had significantly higher cumulative leachate pools of Ca, Mn, Cu, and Pb than Control soil columns. Exchangeable and stable pools of Cu, Pb, and Zn were greater for A. agrestis and L. rubellus soil columns than Control soil columns. However, we estimated that > 98 % of metals from earthworm residues were immobilized in the soil in an exchangeable or stable form over the 60 days using a mass balance approach. Micro-XRF images of longitudinal thin sections of soil columns after 60 days containing A. agrestis confirm metals immobilization in earthworm residues. Our research demonstrates that nutrient and toxic metals are stabilized in soil within earthworm residues.