M. A. Goni

A reassessment of the sources and importance of land-derived organic matter in surface sediments from the Gulf of Mexico

Organic matter in surface sediments from two onshore-offshore transects in the northwestern Gulf of Mexico was characterized by a variety of techniques, including elemental, stable carbon, radiocarbon, and molecular-level analyses. In spite of the importance of the Mississippi River as a sediment source, there is little evidence for a significant terrigenous input based on the low carbon:nitrogen ratios (8 -5) and the enriched d 13 C values of bulk sedimentary organic carbon (219.7‰ to 221.7‰). Radiocarbon analyses, on the other hand, yield depleted D 14 C values (2277‰ to 2572‰) which indicate that a significant fraction of the sedimentary organic carbon (OC) in all these surface sediments must be relatively old and most likely of allochthonous origin. CuO oxidations yield relatively low quantities of lignin products (0.4 -1.4 mg/100 mg OC) along with compounds derived from proteins, polysaccharides, and lipids. Syringyl:vanillyl and cin- namyl:vanillyl ratios (averaging 1.6 and 0.5, respectively) and acid:aldehyde ratios for both vanillyl and syringyl phenols (averaging 0.8 and 1.2, respectively) indicate that the lignin present in sediments originates from nonwoody angiosperm sources and is highly degraded. The d 13 C values of lignin phenols in shelf sediments are relatively depleted in 13 C (averaging 226.3‰) but are increasingly enriched in 13 C at the slope sites (averaging 217.5‰ for the two deepest stations). We interpret these molecular and isotopic compositions to indicate that a significant fraction (

Sources and contribution of terrigenous organic carbon to surface sediments in the Gulf of Mexico

50%) of the lignin and, by inference, the land-derived organic carbon in northwestern Gulf of Mexico sediments ultimately originated from C4 plants. The source of this material is likely to be soil organic matter eroded from the extensive grasslands of the Mississippi River drainage basin. Notably, the mixed C4 and C3 source and the highly degraded state of this material hampers its recognition and quantification in shelf and slope sediments. Our data are consistent with higher than previously estimated inputs of land-derived organic carbon to regions of the ocean, such as the Gulf of Mexico, with significant sources of terrigenous C4-derived organic matter. Copyright

Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico

The sources and burial processes of organic matter in marine sediments are not well understood, yet they are important if we are to have a better understanding of the global carbon cycle. In particular, the nature and fraction of the terrestrial organic carbon preserved in marine sediments is poorly constrained. Here we use the chemical and stable carbon isotope signatures of oxidation products from a macromolecular component (lignin) of the terrigenous organic matter preserved in offshore surface sediments in the Gulf of Mexico to complement similar data from an existing onshore transect in this region. The complete onshore–offshore data set, along with radiocarbon dates of the bulk organic material at the same sites, allows the differentiation of material originating from plants that photosynthesize using the C4 mechanism from those that undergo C3 photosynthesis. We conclude that the offshore lignins derive from erosion of the extensive grassland (C4) soils of the Mississippi River drainage basin, and that the nearshore lignins originate largely from C3 plant detritus from coastal forests and swamps. This distribution is probably due to the hydrodynamic sorting of the different source materials during their seaward transport. These results suggest that previous studies have significantly underestimated the terrigenous fraction of organic matter in offshore sediments by not recognizing the contribution of C4 vegetation to the carbon-isotope composition. Such an underestimate may force revisions in the assessment of past marine primary productivity and associated organic carbon fluxes, and of organic matter preservation/remineralization and nutrient cycling in marine sediments.

Distribution and sources of organic biomarkers in arctic sediments from the Mackenzie River and Beaufort Shelf

Suspended sediments (SS) from the Atchafalaya River (AR) and the Mississippi River and surficial sediment samples from seven shallow cross-shelf transects west of the AR in the northern Gulf of Mexico were examined using elemental (%OC, C/N), isotopic (δ13C, Δ14C), and terrigenous biomarker analyses. The organic matter (OM) delivered by the AR is isotopically enriched (∼−24.5‰) and relatively degraded, suggesting that soil-derived OM with a C4 signature is the predominant OM source for these SS. The shelf sediments display OC values that generally decrease seaward within each transect and westward, parallel to the coastline. A strong terrigenous C/N (29) signal is observed in sediments deposited close to the mouth of the river, but values along the remainder of the shelf fall within a narrow range (8–13), with no apparent offshore trends. Depleted stable carbon isotope (δ13C) values typical of C3 plant debris (−27‰) are found near the river mouth and become more enriched (−22 to −21‰) offshore. The spatial distribution of lignin in shelf sediments mirrors that of OC, with high lignin yields found inshore relative to that found offshore (water depth > 10 m). The isotopic and biomarker data indicate that at least two types of terrigenous OM are deposited within the study area. Relatively undegraded, C3 plant debris is deposited close to the mouth of the AR, whereas more degraded, isotopically enriched, soil-derived OM appears to be deposited along the remainder of the shelf. An important input from marine carbon is found at the stations offshore from the 10-m isobath. Quantification of the terrigenous component of sedimentary OM is complicated by the heterogeneous composition of the terrigenous end-member. A three-end-member mixing model is therefore required to more accurately evaluate the sources of OM deposited in the study area. The results of the mixing calculation indicate that terrigenous OM (soil-derived OM and vascular plant debris) accounts for ∼79% of the OM deposited as inshore sediments and 66% of OM deposited as offshore sediments. Importantly, the abundance of terrigenous OM is 40% higher in inshore sediments and nearly 85% higher in offshore sediments than indicated by a two-end-member mixing model. Such a result highlights the need to reevaluate the inputs and cycling of soil-derived OM in the coastal ocean.

Tannin diagenesis in mangrove leaves from a tropical estuary: A novel molecular approach

Abstract Suspended sediments from the Mackenzie River Delta and surface sediments from the Beaufort Shelf were analyzed by alkaline CuO oxidation. In addition, elemental (percentage total organic carbon, inorganic carbon and silica) and stable carbon isotope compositions were determined for all samples. The carbon-normalized yields of over 60 different compounds derived from the oxidative hydrolysis of several biochemicals, including lignin, cutin, proteins, polysaccharides and lipids were quantified and subjected to principal component analyses (PCA). The results of these investigations indicate that most lignin and cutin products originate from non-woody angiosperm vascular vegetation such as that present in the tundra. For example, lignin-derived product compositions are characterized by relatively high syringyl:vanillyl and cinnamyl:vanillyl phenol ratios (exceeding 0.4 and 0.15, respectively). The compositions of these biomarkers, especially the elevated (0.5 to 1.5) acid:aldehyde ratios for vanillyl and syringyl phenols, also suggest that the land-derived organic matter (OM) exported by the Mackenzie River is highly degraded. Non-lignin CuO reaction products derived from proteins, polysaccharides and lipids display distributions that are consistent with a predominant marine (autochthonous) source. The composition of lipid-derived fatty acid products, which is in shelf sediments are dominated by hexanedecenoic acid, suggests a planktonic origin, likely from diatoms. The distribution of these biomarkers across the shelf indicates the presence of relatively fresh algal remains in at least one sample. The relationships between terrigenous biomarker concentrations and bulk 13 C/ 12 C ratios in surface sediments indicate that terrestrial organic carbon dominates in abundance (80% to 50% of total organic carbon) over much of the shelf. Marine/algal-derived carbon represents 20% to 50% of the total carbon in shelf sediments, with the largest fraction being present in the outer mid-shelf. The large variability in the yields of CuO biomarkers from the river suspended sediment samples highlights the heterogeneous nature of the particle load exported by the Mackenzie River. Such variability must be taken into account during the development of quantitative carbon budgets for the Beaufort Shelf.

Sources and transformations of organic matter in surface soils and sediments from a tidal estuary (North Inlet, South Carolina, USA)

Molecular-level condensed tannin analyses were conducted on a series of mangrove ( Rhizophora mangle) leaves at various stages of decomposition in a tropical estuary. Total molecular tannin yields ranged from 0.5% ash-free dry weight (AFDW) in the most highly degraded black leaves (6 -7 weeks in the water) up to .7% AFDW in fresh leaves (,1 week in the water). Total tannin exhibits an intermediate lability in these leaves relative to other measured biochemicals. Leaching is an important mechanism in tannin removal from leaves as indicated by the 30% loss of measurable tannin during a leaching experiment. Condensed tannin was .80% procyanidin (PC) with the remainder being prodelphinidin (PD). PD tannin, with its higher degree of hydroxylation, proved to be more labile than PC tannin. Average chain length of condensed tannin (degree of polymerization) exhibited an initial increase in response to leaching, but later decreased in the subsequent shift toward abiotic or microbially mediated chemical reactions. Several trends point toward a possible condensation reaction in which tannin plays a role in nitrogen immobilization. These include an apparent inverse correlation between molecular tannin and nitrogen, a positive correlation between molecular tannin and percent basic amino acids, 13 C-NMR data indicating transformation of tannin as opposed to remineralization, and 13 C-NMR data showing loss of condensed tannin B-ring phenolic carbons coupled with preservation of A-ring phenolic carbon. In addition to condensed tannin, the molecular method used also yielded several triterpenoids. Triterpenoids accounted for up to 3.5% AFDW of the leaf material and exhibited a threefold increase between yellow senescent leaves entering the estuary and black leaves. This trend is likely due to the weakening of protective cuticular membranes during leaf decomposition, which leads to increased yields in the acidic conditions used for tannin analyses. Copyright

Constancy in the vegetation of the Amazon Basin during the late Pleistocene: Evidence from the organic matter composition of Amazon deep sea fan sediments

Surface soil and sediment samples collected along a forest-brackish marsh-salt marsh transect in a southeastern U.S. estuary were separated into three different fractions (sand, macro-organic matter, and humus) based on size and density. Elemental, stable carbon isotope, and lignin analyses of these samples reveal important contrasts in the quantity, composition, and sources of organic matter, between forest and marsh sites. Elevated nitrogen contents in humus samples suggest nitrogen incorporation during humification is most extensive in forest soils relative to the marsh sites. The lignin compositions of the macro-organic and humus samples reflect the predominant type of vegetation at each site. Lignin phenol ratios indicate that woody and nonwoody litter from, gymnosperm and angiosperms trees (pines and oaks) is the major source of vascular plant-derived organic matter in the forest site and that angiosperm, grasses (Juncus andSpartina) are the major sources of lignin at the marsh sites. The phenol distributions also reveal that oxidative degradation of lignin is most extensive in the forest and brackish marsh zones whereas little lignin decay occurs in the salt marsh samples. In forest soils, most organic matter originates from highly altered forest vegetation while at the brackish marsh site organic matter is a mixture of degradedJuncus materials and microbial/algal remains. Organic matter in the salt marsh appears to be composed of a more complex mixture of sources, including degradedSpartina detritus as well as algal and microbial inputs. Microbial methane oxidation appears to be an important process and a source of13C depleted organic carbon in subsurface sediments at this site.

Oceanographic considerations for the application of the alkenone-based paleotemperature U37K′ index in the Gulf of California

Analyses of more than 60 sediment samples from the Amazon deep sea fan show remarkably constant terrigenous biomarkers (lignin phenols and cutin acids) and stable carbon isotopic compositions of organic matter (δ\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(^{13}C_{OM}\) \end{document}) deposited from 10 to 70 ka. Sediments from the nine Amazon deep sea fan channel-levee systems investigated in this study yielded relatively narrow ranges for diagnostic parameters such as organic carbon (OC) normalized total lignin yields (Λ = 3.1 ± 1.1 mg/100 mg OC), syringyl:vanillyl phenol ratios (S/V = 0.84 ± 0.06), cinnamyl:vanillyl phenol ratios (C/V = 0.08 ± 0.02), isomeric abundances of cutin-derived dihydroxyhexadecanoic acid (f10,16-OH = 0.65 ± 0.02), and δ\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(^{13}C_{OM}\) \end{document} (−27.6% ± 0.6 ‰). Our measurements support the hypothesis that the vegetation of the Amazon Basin did not change significantly during the late Pleistocene, even during the Last Glacial Maximum. Moreover, the compositions obtained from the Amazon deep sea fan are similar to those of modern Amazon River suspended sediments. Such results strongly indicate that the current tropical rainforest vegetation has been a permanent and dominant feature of the Amazon River watershed over the past 70 k.y. Specifically, we found no evidence for the development of large savannas that had been previously postulated as indicators of increased glacial aridity in Amazonia. Climate models need to be modified to account for the uninterrupted input of moisture to the tropical Amazon region over the late Pleistocene–Holocene period.

Organic matter distribution and accumulation on the inner Louisiana shelf west of the Atchafalaya River

Abstract Alkenone concentrations were determined in sediment trap samples and surficial sediments collected from Guaymas Basin (Gulf of California) to investigate the factors that control the relationship between the U37K′ index and SST. The results from the sediment trap study reveal a positive correlation (r2 = 0.5) between alkenone fluxes and satellite AVHRR sea surface temperature (SST) and a strong correlation (r2 = 0.9) between U37K′ and SST over an annual temperature range of 20°C. Although SST and U37K′ are tightly coupled throughout two upwelling seasons, the relationship deviates from the expression developed by Prahl et al. (1988) at temperatures higher than 26°C. The possible reasons for this deviation are varied but include the observed changes in the coccolithophore species assemblage and the evolution of the thermocline during periods of high SST. The seasonal pattern of alkenone fluxes (higher fluxes during warm periods) observed throughout the 1996 to 1997 study period causes a “bias” in the annually averaged U37K′ record, resulting in temperature estimates that are ∼1°C higher than the annual AVHRR SST average. Furthermore, the U37K′ ratios obtained from core-top sediments indicate an additional ∼2°C “warm bias” in the sedimentary record that may be related to the lateral inputs of alkenones from other regions of the Gulf. These results highlight the importance of oceanographic processes in determining the alkenone temperature signal that is preserved in sediments. After accounting for such effects, U37K′ ratios from a box core were used to reconstruct a SST record extending back to the 18th century for the Guaymas Basin. These results indicate a steady 2°C warming of the surface waters of the Gulf from early 1700s to the 1950s, followed by a rapid apparent 1°C cooling between the 1950s and the 1980s.

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

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