Semester

Summer

Date of Graduation

2022

Document Type

Dissertation

Degree Type

PhD

College

Eberly College of Arts and Sciences

Department

Geology and Geography

Committee Chair

Dorothy J. Vesper

Committee Co-Chair

Christopher Russoniello

Committee Member

Christopher Russoniello

Committee Member

James Lamsdell

Committee Member

Louis McDonald

Committee Member

Ellen Herman

Abstract

Abstract

Chemical characterization of clastic cave sediments and insights into particle transport and storage in karst aquifers

Jill L. Riddell

Cave sediments can be divided into two groups: precipitates and clastics. Precipitates are speleothems, or lithologic or mineral features that are chemically precipitated in the cave environment. Clastic cave sediments are frequently described by depositional facies, sorting, and particle size (Bosch and White, 2004). Robust analytical chemical analyses of these sediments to quantify their physical and chemical components is rarely performed although some chemical characterization of mineralogy and paleomagnetism has become prevalent in recent years (Chess et al., 2010; Sasowsky et al., 2007). The organic carbon content of cave sediments can be representative of organic carbon concentrations in the larger karst system and concentrations of organic carbon in cave sediments can be used to estimate the potential retardation of organic contaminants through the entire karst system. The ability of karst sediments to be a sorbent for metals and organic contaminants, and store and transport contaminants is positively correlated with the amount of organic carbon in the sediment; yet these concentrations are rarely reported in karst sediments. This dissertation seeks to fill the gap in the mineralogy and chemical components of cave sediments; quantify the organic carbon content of cave sediments relative to depositional facies; and measure the adsorption of an organic microsphere onto a cave sediment to explore sediment-contaminant interactions.

A case study from Dropping Lick Cave in Monroe County, WV, is presented where a variety of analytical techniques were used to determine the active fraction ( < 2mm) mineralogy and chemical components of the sediment The sediments were silt and sand-sized particles consisting of quartz, some clay or silicate minerals, dolomite, and amorphous materials. The particle size and total carbon was within the same range reported for the < 2mm fraction in other clastic cave sediments in this region, in the central United States, and in Puerto Rico. The preliminary mineralogy of the sediments is congruent with the mineralogy of surrounding siliciclastic rocks indicating that the source of the sediment is erosional products from nearby Peters Mountain and its slopes.

Particle size, TOC, and total nitrogen were measured in sediments representing different facies in Butler Cave, Virginia, USA. TOC concentrations ranged from 0.08 – 0.87 weight percent and C:N molar ratio ranged from 3 – 15, indicating a possible terrestrial source of organic carbon in these sediments. TOC concentrations measured in Butler Cave were within the same range as those observed in above water, eogenetic clastic cave sediments from two caves in Puerto Rico. Estimated retardation factors calculated based on the TOC concentrations in the Butler Cave sediments indicate the range of TOC in this cave could be responsible for 39 – 987% increase in retardation of selected contaminants. This study highlights the importance of measuring the ranges of TOC in clastic cave sediments across different facies and their role in contaminant fate and transport. In this study,

The adherence of carboxylated and nonfunctionalized polystyrene microspheres onto a clastic cave sediment was quantified for microsphere dilutions in three water types – deionized water, a 25 mg/L CaCO3 solution, and a karst spring water. Regardless of water type, both types of microspheres adhered to the sediment. Infrared absorbance data of different microsphere-solution-sediment mixtures indicated the potential presence of sediment minerals and microspheres in the solution. Analysis of solution pH and infrared spectra suggested pH and mineral constituents of the sediment are the most important factors in microsphere adherence. Using the adherence data, estimated KOC values for both types of microspheres were calculated and were in the same ranges as phthalates, a known contaminant in karst aquifers that is also considered a plastic, like polystyrene. The chemical and physical commonalities between microspheres and organic and microplastic (MP) contaminants warrant further investigation of microspheres as a proxy for contaminants in sediment-contaminant experiments. The results of these experiments suggest that consideration of MPs adhered to sediments should be considered when quantifying MP contamination in karst systems.

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