Isotopic constraints on the sources and associations of organic compounds in marine sediments

Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2006To provide a new perspective on the fate of both natural organic matter and hydrophobic organic contaminants (HOCs) in marine sediments, we have investigated the relationship between radiocarbon (14C) age and the different modes of association in aquatic sediments and soils. Radiocarbon is a sensitive tracer of OM provenance, with variations in its natural abundance reflecting the age and origin of material. The main objective has been to determine the significance of these associations, and to assess how they affect the transport, bioavailability, preservation and residence times of organic compounds in the environment. Our results indicate that the majority of HOCs that persist in marine sediments are solvent-extractable and incorporation into insoluble sediment residues is not quantitatively significant. For pristine sediments, systematic variations in 14C content are observed between different chemically defined sedimentary organic fractions. These variations are dependent on organic matter inputs and/or the affects of diagenesis. Our observations also provide evidence for the protection of labile marine carbon by chemical binding. Finally, the persistence of n-alkanes from biogenic sources compared to those derived from petroleum indicates that protective matrix association can play a crucial role in determining the long-term fate of a compound. Overall, it is clear that both natural organic compounds and HOCs can undergo very different fates depending on their mode of introduction to, and physical disposition in environmental matrices.Funding for this research was provided by the National Science Foundation, CHE-0089172 to T.I. Eglinton and C.M. Reddy, and OCE-82567700 to T.I. Eglinton. I received support from a Charles Davis Hollister Fellowship from Woods Hole Oceanographic Institution

Relationships between carbon isotopic composition and mode of binding of natural organic matter in selected marine sediments

Author Posting. © Elsevier B.V., 2007. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 38 (2007):1824-1837, doi:10.1016/j.orggeochem.2007.07.008.We have investigated the relationships between radiocarbon (14C) and stable carbon (13C) isotopic composition and the different modes of binding of organic matter (OM) present in surficial sediments from near-shore and continental margin sites that vary in terms of input and depositional conditions. To improve our understanding of the entire OM pool, isotopic analysis of sedimentary sub-fractions, as opposed to individual compounds, was performed. This was achieved by sequentially treating sediments by solvent extraction to examine unbound compounds, followed by saponification to cleave ester linked moieties. Isotopic analysis was then performed on the bulk sediment and resulting residues. The molecular composition of the extracts was examined using gas chromatography/mass spectrometry (GC/MS), and the relative contributions of terrestrial and marine biomarkers were assessed. Radiocarbon abundances (Δ14C) of the bulk sediment reflect a mixture of modern, pre-aged and fossil carbon. Offsets in Δ14C between the bulk sediment and sediment residues demonstrate varying associations of these carbon pools. For the majority of sites, a negative offset between extracted (EX2 RES) and saponified (SA-RES) sediment 1 residues results from the removal of relatively 4C-rich material during saponification. Saponification extracts (SAEs) are mainly composed of short chain (n-C12 to n-C24) alkanoic acids with an even/odd dominance indicating a predominantly marine algal or microbial source. This provides evidence for the protection of labile marine carbon by chemical binding. This study aims to bridge the gap between molecular level and bulk OM analyses in marine sediments.The work was supported by funds from the National Science Foundation (CHE-0089172; OCE-0526268)

Evidence of Range Shifts in Riparian Plant Assemblages in Response to Multidecadal Streamflow Declines

Riparian corridors are thought to form hydrological refugia that may buffer species and communities against regional climate changes. In regions facing a warming and drying climate, however, the hydrological regime driving riparian communities is also under threat. We examined recruitment in response to streamflow declines for species inhabiting the riparian zone in southwest Western Australia, testing the extent to which the riparian system has buffered riparian communities from the drying climate. We stratified 49 vegetation transects across the >600 mm per annum regional rainfall gradient encompassed by the Warren River Catchment. Local hydrological conditions were estimated over two 10-year periods; 1980–1989, and 2001–2010, to quantify changes in the flood regime. Mixed effects models tested the relationship between rainfall and flooding on the relative frequency of immature to mature individuals of 17 species of trees and shrubs common to the riparian zones. At the low-rainfall extent of their geographic range, the relative frequency of immature riparian species decreased with declining flow, whereas at the high-rainfall extent of their geographic range the relative frequency of immature individuals increased with declining flow. These results suggest that the geographic ranges of riparian species may be contracting at the low-rainfall margin of their range, while at the high-rainfall margin of their geographic range, reduced flooding regimes appear to be opening up new habitat suitable for recruitment and narrowing the river corridor. No such patterns were observed in upland species, suggesting the river may be buffering upland species. We discuss these findings and their implications for ongoing management and species conservation in a region projected to face further, significant rainfall declines

Hurricane Isaac brings more than oil ashore: Characteristics of beach deposits following the Deepwater Horizon spill.

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Lemkau, K. L., Reddy, C. M., Carmichael, C. A., Aeppli, C., Swarthout, R. F., & White, H. K. Hurricane Isaac brings more than oil ashore: Characteristics of beach deposits following the Deepwater Horizon spill. Plos One, 14(3), (2019):e0213464, doi:10.1371/journal.pone.0213464.Prior to Hurricane Isaac making landfall along the Gulf of Mexico coast in August 2012, local and state officials were concerned that the hurricane would mobilize submerged oiled-materials from the Deepwater Horizon (DWH) spill. In this study, we investigated materials washed ashore following the hurricane to determine if it affected the chemical composition or density of oil-containing sand patties regularly found on Gulf Coast beaches. While small changes in sand patty density were observed in samples collected before and after the hurricane, these variations appear to have been driven by differences in sampling location and not linked to the passing of Hurricane Isaac. Visual and chemical analysis of sand patties confirmed that the contents was consistent with oil from the Macondo well. Petroleum hydrocarbon signatures of samples collected before and after the hurricane showed no notable changes. In the days following Hurricane Isaac, dark-colored mats were also found on the beach in Fort Morgan, AL, and community reports speculated that these mats contained oil from the DWH spill. Chemical analysis of these mat samples identified n-alkanes but no other petroleum hydrocarbons. Bulk and δ13C organic carbon analyses indicated mat samples were comprised of marshland peat and not related to the DWH spill. This research indicates that Hurricane Isaac did not result in a notable change the composition of oil delivered to beaches at the investigated field sites. This study underscores the need for improved communications with interested stakeholders regarding how to differentiate oiled from non-oiled materials. This is especially important given the high cost of removing oiled debris and the increasing likelihood of false positives as oiled-materials washing ashore from a spill become less abundant over time.The authors wish to acknowledge support for this project from the Gulf of Mexico Research Initiative (RFP-V), the Deep-C Consortium (SA 16-30), NSF (OCE-1333148) awarded to CMR, and a Gulf Research Program Early-Career Research Fellowship to HKW. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript