Geology topics

Donald L. Macalady

Publications and source records attributed to Donald L. Macalady.

6 recordsLinked to original sources

USGS2011

Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

ACS Symposium Series↗

USGS2010

The importance of the riparian zone and in-stream processes in nitrate attenuation in undisturbed and agricultural watersheds – a review of the scientific literature

We reviewed published studies from primarily glaciated regions in the United States, Canada, and Europe of the (1) transport of nitrate from terrestrial ecosystems to aquatic ecosystems, (2) attenuation of nitrate in the riparian zone of undisturbed and agricultural watersheds, (3) processes contributing to nitrate attenuation in riparian zones, (4) variation in the attenuation of nitrate in the riparian zone, and (5) importance of in-stream and hyporheic processes for nitrate attenuation in the stream channel. Our objectives were to synthesize the results of these studies and suggest methodologies to (1) monitor regional trends in nitrate concentration in undisturbed 1st order watersheds and (2) reduce nitrate loads in streams draining agricultural watersheds. Our review reveals that undisturbed headwater watersheds have been shown to be very retentive of nitrogen, but the importance of biogeochemical and hydrological riparian zone processes in retaining nitrogen in these watersheds has not been demonstrated as it has for agricultural watersheds. An understanding of the role of the riparian zone in nitrate attenuation in undisturbed watersheds is crucial because these watersheds are increasingly subject to stressors, such as changes in land use and climate, wildfire, and increases in atmospheric nitrogen deposition. In general, understanding processes controlling the concentration and flux of nitrate is critical to identifying and mapping the vulnerability of watersheds to water quality changes due to a variety of stressors. In undisturbed and agricultural watersheds we propose that understanding the importance of riparian zone processes in 2nd order and larger watersheds is critical. Research is needed that addresses the relative importance of how the following sources of nitrate along any given stream reach might change as watersheds increase in size and with flow: (1) inputs upstream from the reach, (2) tributary inflow, (3) water derived from the riparian zone, (4) groundwater from outside the riparian zone (intermediate or regional sources), and (5) in-stream (hyporheic) processes.

Journal of Hydrology↗

USGS2009

New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic matter (NOM)

This paper reports the use of excitation-emission matrix fluorescence spectroscopy (EEMS), parallel factor statistical analysis (PARAFAC), and oxidation-reduction experiments to examine the effect of redox conditions on PARAFAC model results for aqueous samples rich in natural organic matter. Fifty-four aqueous samples from 11 different geographic locations and two plant extracts were analyzed untreated and after chemical treatments or irradiation were used in attempts to change the redox status of the natural organic matter. The EEMS spectra were generated and modeled using a PARAFAC package developed by Cory and McKnight (2005). The PARAFAC model output was examined for consistency with previously reported relations and with changes expected to occur upon experimental oxidation and reduction of aqueous samples. Results indicate the implied fraction of total sample fluorescence attributed to quinone-like moieties was consistent (0.64 to 0.78) and greater than that observed by Cory and McKnight (2005). The fraction of the quinone-like moieties that was reduced (the reducing index, RI) showed relatively little variation (0.46 to 0.71) despite attempts to alter the redox status of the natural organic matter. The RI changed little after reducing samples using zinc metal, oxidizing at high pH with air, or irradiating with a Xenon lamp. Our results, however, are consistent with the correlations between the fluorescence indices (FI) of samples and the ratio of PARAFAC fitting parameters suggested by Cory and McKnight (2005), though we used samples with a much narrower range of FI values.

Aquatic Sciences↗

USGS2007

Field methods for measurement of ground water redox chemical parameters

An inexpensive, versatile, and portable system is presented, which facilitates rapid field determinations of redox potentials, pH, conductivity, ferrous and total iron, nitrite, specific conductance, dissolved oxygen, and temperature. Accuracy is facilitated by on‐site measurements of most parameters using specially constructed flow‐through cells and, for several analyses, sealed reagent ampoules, which can be broken and developed inside a flowing stream of ground water. Coupled with laboratory analyses of more stable ground water parameters, this system can provide accurate and relatively inexpensive determinations of redox conditions in ground water.

Groundwater Monitoring & Remediation↗

USGS1999

The interaction of natural organic matter with iron in a wetland (Tennessee Park, Colorado) receiving acid mine drainage

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

Aquatic Geochemistry↗

USGS1992

Identification of persistent anionic surfactant-derived chemicals in sewage effluent and groundwater

Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13 C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3–10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F 300-50 groundwater have a minimum residence time in the range of 2.7–4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50–500 half lives.

Journal of Contaminant Hydrology↗