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.

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 (14C) 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) 14C 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 14C 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.

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