Carbon-13 depletion in a hydrothermal vent mussel: suggestion of a chemosynthetic food source.

Tissues of a mytilid mussel from the Clambake I hydrothermal vent in the Galápagos Rift zone are strikingly depleted in carbon-13 relative to the tissues of other marine organisms. The stable carbon isotope composition of this mussel suggests that chemoautotrophic bacteria present in the hydrothermal waters are a major food source for filter-feeding organisms in this abyssal environment.

Organic carbon composition of marine sediments: effect of oxygen exposure on oil generation potential.

Anaerobic sedimentary conditions have traditionally been linked to the generation of the source rocks for petroleum formation. However, the influence of sedimentary redox conditions on the composition of freshly deposited organic matter (OM) is not clear. We assessed the effect of in situ exposure time to oxic conditions on the composition of OM accumulating in different coastal and deep-sea sediments using solid-state 13C nuclear magnetic resonance (NMR). 13C NMR spectra were resolved into mixtures of model components to distinguish between alkyl carbon present in protein and nonprotein structures. There is an inverse relation between the length of exposure to oxic conditions and the relative abundance of nonprotein alkyl (alkylNP) carbon, whose concentration is two orders of magnitude higher in coastal sediments with short exposure times than in deep-sea sediments with long exposure times. All alkylNP-rich samples contain a physically separate polymethylene component similar in composition to algaenans and kerogens in type I oil shales. The duration of exposure to oxic conditions appears to directly influence the quality and oil generation potential of OM in marine shales.

Lignin signature of aquatic humic substances.

Lignin-derived phenols dominate the cupric oxide oxidation products of dissolved humic substances from river and lake waters. The relative distributions of these phenols suggest the presence of intact, though oxidized, lignin, which is indicative of the locally dominant vascular plant vegetation. Recognizable lignin is present mostly in humic acid as opposed to fulvic acid fractions. This lignin component represents a source-specific and process-dependent tracer that can uniquely characterize dissolved organic matter.

Bulk chemical characteristics of dissolved organic matter in the ocean.

Dissolved organic matter (DOM) is the largest reservoir of reduced carbon in the oceans. The nature of DOM is poorly understood, in part, because it has been difficult to isolate sufficient amounts of representative material for analysis. Tangential-flow ultrafiltration was shown to recover milligram amounts of >1000 daltons of DOM from seawater collected at three depths in the North Pacific Ocean. These isolates represented 22 to 33 percent of the total DOM and included essentially all colloidal material. The elemental, carbohydrate, and carbon-type (by (13)C nuclear magnetic resonance) compositions of the isolates indicated that the relative abundance of polysaccharides was high ( approximately 50 percent) in surface water and decreased to approximately 25 percent in deeper samples. Polysaccharides thus appear to be more abundant and reactive components of seawater DOM than has been recognized.

Pollen and lignin records of late quaternary vegetation, lake washington.

Analyses of lignin oxidation products and pollen for an 11-meter core from Lake Washington provide independent but similar reconstructions of the late Quaternary vegetation in the Puget Lowland. An exception is in sediments of the late Pleistocene where pollen percentages and influx values suggest conifer forest whereas lignin compositions suggest a treeless source region. This dissimilarity appears to result from different major provenances: eolian transport of pollen to the lake from adjacent or downstream drainage basins as opposed to fluvial transport of lignified plant debris only from the Lake Washington drainage basin.

Organic carbon-14 in the Amazon river system.

Coarse and fine suspended particulate organic materials and dissolved humic and fulvic acids transported by the Amazon River all contain bomb-produced carbon-14, indicating relatively rapid turnover of the parent carbon pools. However, the carbon-14 contents of these coexisting carbon forms are measurably different and may reflect varying degrees of retention by soils in the drainage basin.

A Critical Evaluation of Interlaboratory Data on Total, Elemental, and Isotopic Carbon in the Carbonaceous Particle Reference Material, NIST SRM 1649a.

Because of increased interest in the marine and atmospheric sciences in elemental carbon (EC), or black carbon (BC) or soot carbon (SC), and because of the difficulties in analyzing or even defining this pervasive component of particulate carbon, it has become quite important to have appropriate reference materials for intercomparison and quality control. The NIST "urban dust" Standard Reference Material(®) SRM 1649a is useful in this respect, in part because it comprises a considerable array of inorganic and organic species, and because it exhibits a large degree of ((14)C) isotopic heterogeneity, with biomass carbon source contributions ranging from about 2 % (essentially fossil aliphatic fraction) to about 32 % (polar fraction). A primary purpose of this report is to provide documentation for the new isotopic and chemical particulate carbon data for the most recent (31 Jan. 2001) SRM 1649a Certificate of Analysis. Supporting this is a critical review of underlying international intercomparison data and methodologies, provided by 18 teams of analytical experts from 11 institutions. Key results of the intercomparison are: (1) a new, Certified Value for total carbon (TC) in SRM 1649a; (2) (14)C Reference Values for total carbon and a number of organic species, including for the first time 8 individual PAHs; and (3) elemental carbon (EC) Information Values derived from 13 analytical methods applied to this component. Results for elemental carbon, which comprised a special focus of the intercomparison, were quite diverse, reflecting the confounding of methodological-matrix artifacts, and methods that tended to probe more or less refractory regions of this universal, but ill-defined product of incomplete combustion. Availability of both chemical and (14)C speciation data for SRM 1649a holds great promise for improved analytical insight through comparative analysis (e.g., fossil/biomass partition in EC compared to PAH), and through application of the principle of isotopic mass balance.

An improved thermal oxidation method for the quantification of soot/graphitic black carbon in sediments and soils.

Recent findings have confirmed the importance of black carbon (BC) in the global biogeochemical cycles of carbon and oxygen through its important contribution to the slowly cycling organic carbon (OC) pool. Yet, most BC determination methods published to date measure operationally defined BC fractions, oftentimes with a high potential for artifacts and a lack of specificity for one of the two major forms of the BC continuum, soot/graphitic BC (GBC) and char/charcoal BC (CBC). This paper describes a method that reduces the potential for artifacts to accurately and selectively measure the concentration of GBC in complex mineral and organic matrixes. Marine and lacustrine sediments, river sediments, suspended particles, and a marine plankton sample were first demineralized with a mixture of hydrochloric (HCl) and hydrofluoric (HF) acids to expose any biochemical entrapped in a mineral matrix. The hydrolyzable organic matter fraction (mostly proteins and carbohydrates) was then removed with 02-free trifluoroacetic acid and HCl, after which the non-GBC, non-hydrolyzable OC fraction was finally removed by thermal oxidation at 375 degrees C for 24 h. The specificity of the method for GBC was assessed with pure CBC and GBC samples. Detection limit and GBC recovery in spiked samples were 10 mg kg(-1) and approximately 85%, respectively. Typical GBC concentrations measured in a series of natural samples ranged from <10 mg kg(-1) in marine plankton to 0.19% in a riverine sample. These concentrations were lower by as much as 3 orders of magnitude than those obtained by thermal oxidation without demineralization and removal of hydrolyzable organic matter. The improvements presented in this work allow for the accurate and precise measurement of GBC in complex organic and mineral matrixes by eliminating the interference caused by the presence of CBC, residual non-BC OC and minerals, or by the formation of condensation products that could account for as much as 4-6% of total OC. Combined to stable and radioisotope analysis, this improved method should permit quantitative assessments of the role and dynamics of GBC in the global geochemical cycles of carbon and oxygen.

Evidence for non-selective preservation of organic matter in sinking marine particles.

The sinking of particulate organic matter from ocean surface waters transports carbon to the ocean interior, where almost all is then recycled. The unrecycled fraction of this organic matter can become buried in ocean sediments, thus sequestering carbon and so influencing atmospheric carbon dioxide concentrations. The processes controlling the extensive biodegradation of sinking particles remain unclear, partly because of the difficulty in resolving the composition of the residual organic matter at depth with existing chromatographic techniques. Here, using solid-state 13C NMR spectroscopy, we characterize the chemical structure of organic carbon in both surface plankton and sinking particulate matter from the Pacific Ocean and the Arabian Sea. We found that minimal changes occur in bulk organic composition, despite extensive (>98%) biodegradation, and that amino-acid-like material predominates throughout the water column in both regions. The compositional similarity between phytoplankton biomass and the small remnant of organic matter reaching the ocean interior indicates that the formation of unusual biochemicals, either by chemical recombination or microbial biosynthesis, is not the main process controlling the preservation of particulate organic carbon within the water column at these two sites. We suggest instead that organic matter might be protected from degradation by the inorganic matrix of sinking particles.