Total organic carbon concentrations in clastic cave sediments from Butler Cave, Virginia, USA: implications for contaminant fate and transport.

Clastic cave deposits are representative of sediments throughout the karst aquifer and thus are an abundant and accessible resource through which to study the chemistry of karst aquifer. Clastic cave sediments are attributed to depositional facies based on cave location, sorting, and particle size. These facies settings may influence different chemical parameters of the sediments, like concentrations of total organic carbon (TOC). The TOC concentrations in clastic cave sediments have not been well constrained nor has the role of clastic sediments in contaminant fate and transport through karst systems been well described. In this study, 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. The diamicton facies was sandier and but had similar TOC concentrations compared to the channel facies. 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.

Storage and distribution of organic carbon in cave sediments: examples from two caves in the northern karst region of Puerto Rico.

The clastic sediments that accumulate in cave settings can be an important storage reservoir for organic carbon. This study reports on grain size, total organic carbon (TOC) concentrations, and total organic carbon:total organic nitrogen (TOC:TON) ratios measured in sediments from two caves in Puerto Rico. El Tallonal Cave (TAL) is a small cave with a flowing stream; the sediments in TAL were collected from a deposit that is being actively eroded. Clara Cave (CAM) is an upper level of the Río Camuy Cave System; the sediments from CAM were newly deposited by an internal river that rose in response to Hurricane Maria. Sediments collected from both caves were poorly sorted and contained no apparent stratigraphic correlation. CAM sediments contained a larger range in TOC concentrations but were overall lower than TOC in the TAL sediments. In TAL, the TOC concentrations were higher in sediments collected from below the erosional terrace. TOC:TON ratios from sediments at both caves were highly variable, highlighting the heterogeneous deposition and storage of organic matter. Despite the observed variation, TOC concentrations in both cave systems could cause retardation of organic contaminants by up to two orders-of-magnitude, implying that deposited sediments influence the fate of organic contaminants in the groundwater; therefore, cave sediments could facilitate long term storage of organic carbon and associated contaminants.